CN103773379A - Stabilizing agent applicable to soil with combined pollution of heavy metals and semi-volatile organic compounds and use method thereof - Google Patents
Stabilizing agent applicable to soil with combined pollution of heavy metals and semi-volatile organic compounds and use method thereof Download PDFInfo
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- CN103773379A CN103773379A CN201410032709.XA CN201410032709A CN103773379A CN 103773379 A CN103773379 A CN 103773379A CN 201410032709 A CN201410032709 A CN 201410032709A CN 103773379 A CN103773379 A CN 103773379A
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Abstract
The invention discloses a stabilizing agent applicable to soil with combined pollution of heavy metals and semi-volatile organic compounds and a use method thereof. The stabilizing agent comprises the following components in percentage by weight: 5-10% of heavy-metal chelating agent, 10-20% of cementing material, 55-65% of modified clay mineral and 10-15% of alkaline exciting agent, wherein the modified clay mineral is prepared by mixing hexadecyl trimethyl ammonium bromide and sodium lauryl sulfate according to the volume ratio of (1:0.8)-(1:1.2), and then adding the hexadecyl trimethyl ammonium bromide and the sodium lauryl sulfate into the clay mineral. The use method comprises the following steps of: mixing and grinding the cementing material, the modified clay mineral and the alkaline exciting agent till the obtained particles have the Brinell specific area of 5000-8000cm<2>/g, pass through 200 meshes and have the water content less than 3%, and directly adding the obtained mixture into the soil polluted by the heavy metals according to the mass ratio of 10-20%, mixing and stirring; preparing the heavy-metal chelating agent into 10-20% solution, spraying the solution into the soil polluted by the heavy metals, mixing and stirring. The stabilizing agent and the use method disclosed by the invention have the advantages that the traditional cement type components are not used, the leaching toxicity of the treated pollutants is obviously reduced, and the heavy metals and semi-volatile organic pollutants in the soil can be fast stabilized.
Description
Technical field
The invention belongs to contaminated soil repairing and treating technical field, relate to a kind of stablizer and using method thereof that is applicable to heavy metal and the quick repairing and treating of semi-volatile organic matter combined contamination soil.
Background technology
In recent years, the pollution that Industrial-Enterprises in China causes edatope manifests gradually, and pollutent mainly contains heavy metal, volatility and semi-volatile organic matter.How effectively to implement contaminated soil and administer reparation, ensure that the people is healthy and safe, become the focus that the current whole society pays close attention to.
Stabilization technology is comparatively maturation and cost-effective technology of one, aspect the environmental risk of reduction heavy metal and part semi-volatile organic matter, has good effect.This technology is utilized the physics chemical action such as stablizer and soil and pollutent generation chelating wherein, precipitation, absorption, by reducing the transport property of pollutant in soil, thereby reaches the object of repairing and treating.Up to now, in contaminated soil rehablitation project, be widely used at American-European and other developed country's stabilization technologies.
At present, for comparatively ripe containing the stabilization technology of heavy metal class contaminated soil, and it is little to be applied to the stablizer of heavy metal and semi-volatile organic matter combined contamination soil.Compared with heavy metal, semi-volatile organic matter is of a great variety, physics-chem characteristic is more complicated, fixing containing difficulty is large generally, while forming combined contamination soil with heavy metal, difficulty of governance increases, therefore, the stabilization technology of combined contamination soil has many single features containing heavy metal class contaminated soil stabilization technology that are different from, the stablizer that is applicable to heavy metal class contaminated soil can not be used in the reparation of heavy metal and semi-volatile organic matter combined contamination soil, because of its repairing effect to semi-volatile organic matter bad.
The domestic stablizer patent for combined contamination soil is relatively less at present, and mainly concentrates on the patent that adopts the inorganic jointing compound such as cement, lime.The reparation medicament that contains cement constituents is adding to after soil, can cause repairing rear soil hardening, increase-volume, and use merely the inorganic jointing compound such as cement or lime, rely on the C-S-H of hydration reaction formation and the adsorption of clay mineral, not only cannot fully effectively fix organism, the fixed effect of heavy metal in soil is easily subject to the impact of external environmental condition simultaneously.Organism has interference effect for the cementing process of inorganic jointing compound, and the additive that How to choose is suitable is treated as to combined contamination soil the bottleneck that this technology is applied to realize fast and effectively.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of stablizer and using method thereof that is applicable to heavy metal and semi-volatile organic matter combined contamination soil is provided, this stablizer does not use traditional cement class component, and the Leaching of processing after stain thing obviously declines.
Technical scheme of the present invention is as follows:
A kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, this stabilizer package contains the component of following mass ratio: heavy metal chelant 5%～10%, gelling material 10%～20%, modified clay mineral 55%～65%, alkali-activator 10%～15%, and its raw material summation is 100%; Gelling material in said components, modified clay mineral, alkali-activator are ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%; The modified clay mineral that accounts for raw material summation 50%～65% needs preparation separately.
Described modified clay mineral is prepared as follows and obtains:
Preparation cetyl trimethylammonium bromide (CTMAB, a kind of quaternary ammonium cation tensio-active agent) and the mixing solutions of sodium lauryl sulphate (SDS, a kind of anion surfactant), v/v=1:0.8～1:1.2, join in clay mineral with mass ratio 5%～10%, at 40 ℃～50 ℃, shake after 8h～10h, filter, washing, refilter, at 85 ℃～90 ℃, dry 48h～72h, grinds, and crosses 200 mesh sieves.
Described clay mineral is that one or more in zeolite, vermiculite, polygorskite, montmorillonite, kaolin are compound.
Heavy metal chelant in described stablizer is that one or more in EDTA, Iron sulfuret, triazine trisodium salt are compound.
Gelling material in described stablizer is that one or more in silicate, silico-aluminate, ferro-aluminate are compound.
Alkali-activator in described stablizer is sodium sulfate.
The using method of the above-mentioned stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil is as follows:
Gelling material in described stablizer, modified clay mineral, alkali-activator mix and use, and using method is: will the gelling material in described stablizer, modified clay mineral, alkali-activator be ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%; Then the product after mixed grinding is added directly in heavy-metal contaminated soil and mix and blend, adding proportion is soil quality 10%～20%;
The heavy metal chelant that accounts for raw material summation 5%～10% in described stablizer uses separately, using method is: it is 10%～20% solution that the heavy metal chelant in described stablizer is mixed with to mass percentage concentration, then the heavy metal chelating agent solution of preparation is sprayed directly in heavy-metal contaminated soil and mix and blend.
The invention has the beneficial effects as follows:
Main component in the stablizer that the present invention adopts mostly is natural materials, by compound actions such as chelating, complexing, precipitation, absorption, realize at short notice the long-term stability of heavy metal and half volatile organic contaminant, weaken the ecological risk of its contaminated soil, reduce toxicity and the biological effectiveness of pollutent, to reach the object of repairing polluted soil in the short period of time, heavy metal and half volatile organic contaminant stabilization fast after using in soil.The material adopting is cheap and easy to get, and can not produce secondary pollution, can reach comparatively desirable and stable state after 7 days, is a kind of stable curing technology rapidly and efficiently.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation:
Embodiment 1
A kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, this stabilizer package contains the component of following mass ratio: heavy metal chelant EDTA5%, gelling material silicate 20%, modified clay mineral 65%, alkali-activator sodium sulfate 10%, and its raw material summation is 100%;
Described modified clay mineral prepares as follows: the mixing solutions of 1:0.8 preparation cetyl trimethylammonium bromide and sodium lauryl sulphate by volume, join in clay mineral zeolite with mass ratio 5%, at 50 ℃, shake after 8h, filter, washing, refilters, dry 60h at 85 ℃, grind, cross 200 mesh sieves.
Embodiment 2
A kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, this stabilizer package contains the component of following mass ratio: the 1:1 compound 10% of heavy metal chelant EDTA and Iron sulfuret, gelling material silico-aluminate 20%, modified clay mineral 55%, alkali-activator sodium sulfate 15%, and its raw material summation is 100%;
Described modified clay mineral prepares as follows: the mixing solutions of 1:1.2 preparation cetyl trimethylammonium bromide and sodium lauryl sulphate by volume, join in clay mineral vermiculite with mass ratio 10%, at 40 ℃, shake after 10h, filter, washing, refilters, dry 48h at 90 ℃, grind, cross 200 mesh sieves.
Embodiment 3
A kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, this stabilizer package contains the component of following mass ratio: the 1:1 compound 18% of heavy metal chelant Iron sulfuret 8%, gelling material silicate and silico-aluminate, modified clay mineral 62%, alkali-activator sodium sulfate 12%, and its raw material summation is 100%;
Described modified clay mineral prepares as follows: the mixing solutions of 1:1.1 preparation cetyl trimethylammonium bromide and sodium lauryl sulphate by volume, join in clay mineral kaolin with mass ratio 7%, at 45 ℃, shake after 9h, filter, washing, refilters, dry 48h at 88 ℃, grind, cross 200 mesh sieves.
Embodiment 4
A kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, this stabilizer package contains the component of following mass ratio: heavy metal chelant EDTA10%, gelling material silico-aluminate 15%, modified clay mineral 60%, alkali-activator sodium sulfate 15%, and its raw material summation is 100%;
Described modified clay mineral prepares as follows: the mixing solutions of 1:1 preparation cetyl trimethylammonium bromide and sodium lauryl sulphate by volume, join with mass ratio 8% in the 1:1 compound of clay mineral zeolite and montmorillonite, at 45 ℃, shake after 8h, filter, washing, refilters, dry 60h at 85 ℃, grind, cross 200 mesh sieves.
Embodiment 5
A kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, this stabilizer package contains the component of following mass ratio: heavy metal chelant triazine trisodium salt 10%, gelling material ferro-aluminate 10%, modified clay mineral 65%, alkali-activator sodium sulfate 15%, and its raw material summation is 100%;
Described modified clay mineral prepares as follows: the mixing solutions of 1:0.9 preparation cetyl trimethylammonium bromide and sodium lauryl sulphate by volume, join in clay mineral polygorskite with mass ratio 9%, at 50 ℃, shake after 8h, filter, washing, refilters, dry 72h at 85 ℃, grind, cross 200 mesh sieves.
Application test example 1
" a kind of stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil " is in the application of repairing in certain chemical plant contaminated soil
Place is positioned at Chuansha New Town, Pudong New Area, Shanghai, takes up an area 11000 square metres, and former address is Pudong chemical plant.According to the monitoring data in place, principal pollutant in this place soil are heavy metal (copper and zinc), polycyclic aromatic hydrocarbons (benzo (a) pyrene), the maximum value detecting before excavation is respectively: copper 75.8mg/kg, zinc 284mg/kg, benzo (a) pyrene 0.6mg/kg.
Utilize professional excavator to excavate soil, total co-processing 25500 side's contaminated soils, division operation unit, soil is stored up inside temporarily, and set up impervious barrier in mound district, utilize ring hammer crusher that soil is sieved, is evenly distributed on impervious barrier, regulating soil moisture content is 20% left and right.
Use the soil stabilizer described in the embodiment of the present invention 4, will the gelling material in described stablizer, modified clay mineral, alkali-activator be ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%; Then the product after mixed grinding is added directly in heavy-metal contaminated soil and mix and blend, adding proportion is soil quality 12.5%; It is 15% solution that the heavy metal chelant that accounts for raw material summation 10% in described stablizer is mixed with to mass percentage concentration, then the heavy metal chelating agent solution of preparation is sprayed directly in heavy-metal contaminated soil and mix and blend.
After stablizer and soil are stirred, fully mixed, maintenance more than 5 days, is carried out sampling monitoring, the gathering in table 1 of monitoring result and respective standard value.
Table 1 soil remediation Acceptance Monitoring result summary sheet
As can be seen from Table 1, after stabilization treatment in the leach liquor of soil, the maximum value of copper, zinc and benzo (a) pyrene concentration is all well below " groundwater quality standard " IV class standard value (GB/T14848-93), and underground water intervention value in Dutch DIV standard.Illustrate after stabilization treatment, in soil, the Leaching of objectionable impurities is well controlled, and has reached repairing effect and the requirement of expection.
Application test example 2
Use the soil stabilizer described in the embodiment of the present invention 3 at certain contaminated site, will the gelling material in described stablizer, modified clay mineral, alkali-activator be ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%; Then the product after mixed grinding is added directly in heavy-metal contaminated soil and mix and blend, adding proportion is soil quality 10%; It is 10% solution that the heavy metal chelant that accounts for raw material summation 8% in described stablizer is mixed with to mass percentage concentration, then the heavy metal chelating agent solution of preparation is sprayed directly in heavy-metal contaminated soil and mix and blend.
Use soil stabilizer, maintenance, after 7 days, is carried out sampling monitoring, and soil remediation Acceptance Monitoring the results are shown in following table:
| Pollutent | Before excavation, detect maximum value (mg/kg) | Fluid concentration (μ g/L) after repairing |
| Zinc | 1771.5 | Do not detect |
| Nickel | 808.5 | Do not detect |
| Cadmium | 99.1 | Do not detect |
| Chromium | 1530.5 | Do not detect |
| Copper | 1208.5 | Do not detect |
| Benzo (a) pyrene | 0.6 | Do not detect |
| Total petroleum hydrocarbon | 3949.5 | 957 |
Application test example 3
Use the soil stabilizer described in the embodiment of the present invention 1 at certain contaminated site, will the gelling material in described stablizer, modified clay mineral, alkali-activator be ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%; Then the product after mixed grinding is added directly in heavy-metal contaminated soil and mix and blend, adding proportion is soil quality 20%; It is 20% solution that the heavy metal chelant that accounts for raw material summation 5% in described stablizer is mixed with to mass percentage concentration, then the heavy metal chelating agent solution of preparation is sprayed directly in heavy-metal contaminated soil and mix and blend.
Use soil stabilizer, maintenance, after 7 days, is carried out sampling monitoring, and soil remediation Acceptance Monitoring the results are shown in following table:
| Pollutent | Before excavation, detect maximum value (mg/kg) | Steep cencentration (μ g/L) after repairing |
| Arsenic | 122 | Do not detect |
| Cadmium | 41.2 | Do not detect |
| Copper | 116 | Do not detect |
| Mercury | 10.0 | Do not detect |
| Nickel | 71 | Do not detect |
| Zinc | 252 | Do not detect |
| Benzo (a) pyrene | 2.5 | Do not detect |
Claims (6)
1. a stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil, is characterized in that,
This stabilizer package contains the component of following mass ratio: heavy metal chelant 5%～10%, gelling material 10%～20%, modified clay mineral 55%～65%, alkali-activator 10%～15%, and its raw material summation is 100%;
Gelling material in said components, modified clay mineral, alkali-activator are ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%;
Described modified clay mineral is prepared as follows and obtains: the mixing solutions of 1:0.8 by volume～1:1.2 preparation cetyl trimethylammonium bromide and sodium lauryl sulphate, join in clay mineral with mass ratio 5%～10%, at 40 ℃～50 ℃, shake after 8h～10h, filter, washing, refilters, dry 48h～72h at 85 ℃～90 ℃, grind, cross 200 mesh sieves.
2. stablizer as claimed in claim 1, is characterized in that: described clay mineral is that one or more in zeolite, vermiculite, polygorskite, montmorillonite, kaolin are compound.
3. stablizer as claimed in claim 1 or 2, is characterized in that, the heavy metal chelant in described stablizer is that one or more in EDTA, Iron sulfuret, triazine trisodium salt are compound.
4. stablizer as claimed in claim 3, is characterized in that, the gelling material in described stablizer is that one or more in silicate, silico-aluminate, ferro-aluminate are compound.
5. stablizer as claimed in claim 4, is characterized in that, the alkali-activator in described stablizer is sodium sulfate.
6. a using method for the stablizer that is applicable to heavy metal and semi-volatile organic matter combined contamination soil as claimed in claim 1, is characterized in that,
Gelling material in described stablizer, modified clay mineral, alkali-activator mix and use, and using method is: will the gelling material in described stablizer, modified clay mineral, alkali-activator be ground to Blain specific surface 5000～8000cm after mixing
2/ g, crosses 200 mesh sieves, and water ratio is less than 3%; Then the product after mixed grinding is added directly in heavy-metal contaminated soil and mix and blend, adding proportion is soil quality 10%～20%;
The heavy metal chelant that accounts for raw material summation 5%～10% in described stablizer uses separately, using method is: it is 10%～20% solution that the heavy metal chelant in described stablizer is mixed with to mass percentage concentration, then the heavy metal chelating agent solution of preparation is sprayed directly in heavy-metal contaminated soil and mix and blend.
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Cited By (15)
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| CN104174645A (en) * | 2014-08-29 | 2014-12-03 | 四川普丽环保科技有限公司 | Method for remedying heavy metal pollution of soil by using calcium silicate hydrate generated by treating silicon tetrachloride |
| CN105295936A (en) * | 2014-11-07 | 2016-02-03 | 上海市环境科学研究院 | Heavy metal combined pollution soil remediation agent based on modified clay and preparation method of agent |
| CN105838381A (en) * | 2016-04-26 | 2016-08-10 | 湖南中大建设工程检测技术有限公司 | Soil improver and method for improving soil |
| CN106010563A (en) * | 2016-06-17 | 2016-10-12 | 战锡林 | Aniline contaminated soil remediation agent |
| CN106118683A (en) * | 2016-06-30 | 2016-11-16 | 山东爱福地生物科技有限公司 | A kind of heavy-metal contaminated soil renovation agent |
| CN106893590A (en) * | 2017-02-17 | 2017-06-27 | 浩蓝环保股份有限公司 | A kind of heavy metal-polluted soil passivation stabilizer and preparation method thereof and application method |
| WO2017173737A1 (en) * | 2016-04-06 | 2017-10-12 | 北京高能时代环境技术股份有限公司 | Stabilizing agent for treating chromium contaminated soil and application thereof |
| CN109054856A (en) * | 2018-09-16 | 2018-12-21 | 安徽乐农环保科技有限公司 | Soil modification clay mineral and preparation method thereof |
| CN109663583A (en) * | 2019-01-25 | 2019-04-23 | 兰州大学 | A kind of material and preparation method thereof of adsorbing separation heavy metal ions in soil |
| CN110340135A (en) * | 2019-07-22 | 2019-10-18 | 鸿灌环境技术有限公司 | A kind of method contaminated soil conditioning and repaired |
| CN110732549A (en) * | 2019-10-23 | 2020-01-31 | 深圳研源环境科技有限公司 | Heavy metal and pesticide composite polluted soil treatment process |
| CN112047682A (en) * | 2020-08-21 | 2020-12-08 | 浙江博世华环保科技有限公司 | Heavy metal solidification stabilizing agent and preparation method and application thereof |
| CN112322304A (en) * | 2020-11-13 | 2021-02-05 | 浙江正峰生态环境工程有限公司 | Passivator and passivation method for soil heavy metal pollution treatment |
| CN113399449A (en) * | 2021-06-18 | 2021-09-17 | 西安建筑科技大学 | Environment-friendly reinforcing method for inhibiting dust emission in heavy metal polluted site |
| CN117138610A (en) * | 2023-10-27 | 2023-12-01 | 成都理工大学 | Method for inhibiting dissolution of clay in carbonate rock |
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| CN104174645A (en) * | 2014-08-29 | 2014-12-03 | 四川普丽环保科技有限公司 | Method for remedying heavy metal pollution of soil by using calcium silicate hydrate generated by treating silicon tetrachloride |
| CN105295936A (en) * | 2014-11-07 | 2016-02-03 | 上海市环境科学研究院 | Heavy metal combined pollution soil remediation agent based on modified clay and preparation method of agent |
| CN105295936B (en) * | 2014-11-07 | 2018-09-11 | 上海市环境科学研究院 | A kind of heavy-metal composite pollution soil remediation medicament and preparation method thereof based on modified clay |
| WO2017173737A1 (en) * | 2016-04-06 | 2017-10-12 | 北京高能时代环境技术股份有限公司 | Stabilizing agent for treating chromium contaminated soil and application thereof |
| CN105838381A (en) * | 2016-04-26 | 2016-08-10 | 湖南中大建设工程检测技术有限公司 | Soil improver and method for improving soil |
| CN106010563A (en) * | 2016-06-17 | 2016-10-12 | 战锡林 | Aniline contaminated soil remediation agent |
| CN106118683A (en) * | 2016-06-30 | 2016-11-16 | 山东爱福地生物科技有限公司 | A kind of heavy-metal contaminated soil renovation agent |
| CN106893590A (en) * | 2017-02-17 | 2017-06-27 | 浩蓝环保股份有限公司 | A kind of heavy metal-polluted soil passivation stabilizer and preparation method thereof and application method |
| CN109054856A (en) * | 2018-09-16 | 2018-12-21 | 安徽乐农环保科技有限公司 | Soil modification clay mineral and preparation method thereof |
| CN109663583A (en) * | 2019-01-25 | 2019-04-23 | 兰州大学 | A kind of material and preparation method thereof of adsorbing separation heavy metal ions in soil |
| CN110340135A (en) * | 2019-07-22 | 2019-10-18 | 鸿灌环境技术有限公司 | A kind of method contaminated soil conditioning and repaired |
| CN110732549A (en) * | 2019-10-23 | 2020-01-31 | 深圳研源环境科技有限公司 | Heavy metal and pesticide composite polluted soil treatment process |
| CN110732549B (en) * | 2019-10-23 | 2022-06-28 | 深圳研源环境科技有限公司 | Heavy metal and pesticide composite polluted soil treatment process |
| CN112047682A (en) * | 2020-08-21 | 2020-12-08 | 浙江博世华环保科技有限公司 | Heavy metal solidification stabilizing agent and preparation method and application thereof |
| CN112047682B (en) * | 2020-08-21 | 2022-03-25 | 浙江博世华环保科技有限公司 | Heavy metal solidification stabilizing agent and preparation method and application thereof |
| CN112322304A (en) * | 2020-11-13 | 2021-02-05 | 浙江正峰生态环境工程有限公司 | Passivator and passivation method for soil heavy metal pollution treatment |
| CN113399449A (en) * | 2021-06-18 | 2021-09-17 | 西安建筑科技大学 | Environment-friendly reinforcing method for inhibiting dust emission in heavy metal polluted site |
| CN117138610A (en) * | 2023-10-27 | 2023-12-01 | 成都理工大学 | Method for inhibiting dissolution of clay in carbonate rock |
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Application publication date: 20140507 |