CN104289514B - Heavy metal technique in a kind of circular flow field intensity Nanoscale Iron rehabilitating soil - Google Patents
Heavy metal technique in a kind of circular flow field intensity Nanoscale Iron rehabilitating soil Download PDFInfo
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Abstract
A heavy metal technique in circular flow field intensity Nanoscale Iron rehabilitating soil, belongs to technical field of soil remediation.Comprise the following steps: CMC is dissolved in distilled water by (1), be placed in starvation container, constant temperature vibration heats, and passes into nitrogen, by FeSO in CMC solution
47H
2o solution adds in CMC solution and stirs, by NaBH
4dropwise also at the uniform velocity instills, at the uniform velocity isothermal vibration, obtained stabilisation nano zero valence iron suspension; (2) bore at soil region and dig and add well; (3) with circulating pump, stabilisation nano zero valence iron suspension is injected feed tube, enter Injection Well and extraction well, rear time-out, extracting from extraction well, inject in Injection Well, until during 24h, stop injecting; (4) from extraction well, extract reduction liquid and inject to Injection Well, carrying out thermostatic process, adding acid-base buffer with heating rod and temperature controller to reduce liquid, the pH value of liquid is reduced in adjustment.The present invention has can promote that nano zero valence iron realizes reduction to the heavy metal in soil, eliminates the advantages such as the toxicity of heavy metal ion.
Description
Technical field
The invention belongs to the technical field of soil remediation of field of environment pollution control, be specifically related to the heavy metal technique in a kind of circular flow field intensity Nanoscale Iron rehabilitating soil
Background technology
Heavy metal pollution of soil is one of the key problem in Environmental Protection in China field.Heavy metal pollution of soil difficulty of governance is large, has disguise, hysteresis quality.The research of soil pollution and recovery technique thereof has very strong realistic meaning and value at a specified future date.Although existing a lot of soil restoring technology in recent years, comprise physical treatment method (physical partition method, soil moved in improve the original or plough deeply method, solidification method and solidify & bury method, steam soaking formulation, thermal desorption method); Chemical treatment method (chemical amendments, oxidizing process, reducing process, chemical leaching method, solvent extraction method, electro reclamation method); Bioremediation (plant, animal, microorganism remediation technology) etc., but can low cost, the technology of high efficiency application few.
Nano zero valence iron (nZVI) in-situ reducing recovery technique belongs to the category of in-situ chemical reducing process, has the advantages such as the pollutant scope that equipment is simple, implementation cost is low, be suitable for is wide, reparation speed is fast, efficiency is high, the applicable degree of depth is large.But, common nanometer iron powder character is enlivened, be easy to oxidation occurs or assembles agglomerating, the method improving nano-iron particle stability is in recent years generally the stabilisation adopting CMC (sodium carboxymethylcellulose) to realize Nanoscale Iron, but has that CMC dosage is large, poor fluidity, affect the shortcomings such as large by solution acid-basicity.Only adopt CMC to carry out stabilisation to Nanoscale Iron, be difficult to the non-homogeneous contaminated site or the clay place that adapt to artificial formation.
Summary of the invention
The object of the invention is for solving the stabilisation adopting sodium carboxymethylcellulose to realize Nanoscale Iron, have that dosage is large, poor fluidity, affect the shortcomings such as large by solution acid-basicity, there is provided a kind of and can promote that nano zero valence iron realizes reduction to the heavy metal in soil, eliminate the heavy metal technique in the circular flow field intensity Nanoscale Iron rehabilitating soil of the toxicity of heavy metal ion.
The present invention is the technical scheme taked that solves the problem:
Heavy metal technique in a kind of circular flow field intensity of the present invention Nanoscale Iron rehabilitating soil, comprises the following steps:
(1) first take sodium carboxymethylcellulose 0.01 ~ 0.02L that mass percent concentration is 0.8 ~ 1.0%, be dissolved in distilled water, be placed in the container of starvation, heat under constant temperature vibration condition, obtained carboxymethylcellulose sodium solution; Then in carboxymethylcellulose sodium solution, pass into high pure nitrogen, high pure nitrogen flow velocity is 50 ~ 80mL/min, and the time is 20 ~ 25min, is the FeSO of 0.01 ~ 0.02mol/L by pre-configured concentration
47H
2o solution adds and passes in the carboxymethylcellulose sodium solution of high pure nitrogen, under high pure nitrogen protection, fully stir 20 ~ 30min under constant temperature, is the NaBH of 0.03 ~ 0.05mol/L in whipping process by concentration
4solution also dropwise and at the uniform velocity instill in the container of starvation, continues at the uniform velocity isothermal vibration 15 ~ 25min, and obtained stabilisation nano zero valence iron suspension, the concentration of the obtained Fe contained by stabilisation nano zero valence iron suspension is 0.10 ~ 0.30g/L, wherein FeSO
47H
2o solution and NaBH
4the addition of solution calculates according to the content of beary metal in soil to be repaired;
(2) section is added the soil region that need administer is selected, bore at selected cross section place place and dig transverse direction and longitudinal separation is 1.5 ~ 2.0m, diameter be 60 ~ 100mm add well, that is arranged by odd number adds well as " Injection Well ", even rows add well as " extraction well ", and form " Injection Well " in a row form spaced with " extraction well ", the degree of depth of " Injection Well " and " extraction well " is as the criterion to reach bottom the soil horizon that need administer simultaneously, perforation floral tube is preset in " Injection Well " with " extraction well ", and floral tube diameter is 55 ~ 95mm, penetration hole diameter is 8 ~ 10mm, pitch of holes is 30 ~ 40mm,
(3) with the stabilisation nano zero valence iron suspension that step (1) obtains by circulating pump, inject feed tube, then " Injection Well " is entered with " extraction well ", inject flow control at 0.2 ~ 0.5mL/min, injection length is 2 ~ 4h, complete rear time-out 2 ~ 3h to be implanted, from " extraction well ", with the flow velocity of 0.2 ~ 0.3mL/min, extracting is carried out to stabilisation nano zero valence iron suspension, and with the flow velocity of 0.2 ~ 0.3mL/min, stabilisation nano zero valence iron suspension is injected in " Injection Well ", injection length is 1.5 ~ 2h, again suspend 2 ~ 3h, repeat to inject circulation, suspend, to reinject circulation, pause step again, until during 24h, thorough stopping is injected,
(4) the reduction liquid extracted from " extraction well " is put into fluid storage tank, and inject reduction liquid to " Injection Well ", and fluid storage tank keeps starvation, simultaneously, thermostatic process is carried out with heating rod and temperature controller to reducing liquid in fluid storage tank, add appropriate acid-base buffer, regulating the acid-base value of reduction liquid to remain on pH value is 6.5 ~ 7.0 simultaneously.
Described acid-base buffer is the hydrochloric acid of 0.8 ~ 1.0mol/L and the sodium acid carbonate mixed liquor of 0.2 ~ 0.5mol/L.
The present invention adopts technique scheme, compared with prior art has following beneficial effect:
(1) the reducing agent circulation flow field adopting pressure current to be formed, the mobility of reinforced nano iron reducer, simultaneously by CMC dispersant, implements decentralized stabilization to nano zero valence iron, the heavy metal in reduction rehabilitating soil.This technology can be described as " hydraulics-chemistry " combines fluidization technology, namely adopts hydraulic principle, under " Injection Well " effect with " extraction well ", Nanoscale Iron reducing agent is flowed passively in soil.In order to impel its smooth flow, adopt decentralized as chemical dispersant aided nano iron particle of CMC.Improve the decentralization of nanometer nulvalent iron particle in non-sandy soil or clayed soil, and continuing of reducing agent stability can be promoted, improve the effect of nano zero-valence Fe3+ reduction heavy metal in soil ion.
(2) the stabilisation nano zero valence iron suspension that the present invention adopts is not simple disposable injection, but injects in two stages.Utilize circulating pump, from extraction well, extracting is carried out to stabilisation nano zero valence iron suspension, in " Injection Well ", stabilisation nano zero valence iron suspension is injected, in soil certain depth region, form circulation flow field.Stabilisation nano zero valence iron suspension now in soil is no longer resting state, but is in " intermittent flow is dynamic ".
(3) in fluid storage tank, constant temperature process is carried out to reduction liquid, carry out acid-base value simultaneously and continue to regulate, maintain Nanoscale Iron reducing solution active and stability for a long time.
(4) the inventive method is easy, and equipment is simple, is beneficial to site operation.Be applicable to the artificial non-homogeneous thin matter, opaque or the cement soil layer pollution amelioration that are formed, be also applicable to the dry soil pollution amelioration that water content is lower.
Detailed description of the invention
Embodiment 1
Heavy metal technique in a kind of circular flow field intensity of the present embodiment Nanoscale Iron rehabilitating soil, comprises the following steps:
(1) first take the sodium carboxymethylcellulose 0.01L that mass percent concentration is 0.8%, be dissolved in distilled water, be placed in the container of starvation, heat under constant temperature vibration condition, obtained carboxymethylcellulose sodium solution; Then in carboxymethylcellulose sodium solution, pass into high pure nitrogen, high pure nitrogen flow velocity is 50mL/min, and the time is 20min, is the FeSO of 0.01mol/L by pre-configured concentration
47H
2o solution adds and passes in the carboxymethylcellulose sodium solution of high pure nitrogen, under high pure nitrogen protection, fully stir 20min under constant temperature, is the NaBH of 0.03mol/L in whipping process by concentration
4solution also dropwise and at the uniform velocity instill in the container of starvation, continues at the uniform velocity isothermal vibration 15min, and obtained stabilisation nano zero valence iron suspension, the concentration of the obtained Fe contained by stabilisation nano zero valence iron suspension is 0.10g/L, wherein FeSO
47H
2o solution and NaBH
4the addition of solution calculates according to the content of beary metal in soil to be repaired;
(2) choosing is the chromium slag contaminated site soil of 0.1g/kg containing Cr (VI) concentration, select at the soil region that need administer and add section, bore at selected cross section place place and dig transverse direction and longitudinal separation is 1.5m, diameter be 60mm add well, that is arranged by odd number adds well as " Injection Well ", even rows add well as " extraction well ", and form " Injection Well " in a row form spaced with " extraction well ", the degree of depth of " Injection Well " and " extraction well " is as the criterion to reach bottom the soil horizon that need administer simultaneously, perforation floral tube is preset in " Injection Well " with " extraction well ", and floral tube diameter is 55mm, penetration hole diameter is 8mm, pitch of holes is 30mm,
(3) with the stabilisation nano zero valence iron suspension that step (1) obtains by circulating pump, inject feed tube, then " Injection Well " is entered with " extraction well ", inject flow control at 0.2mL/min, injection length is 2h, complete rear time-out 2h to be implanted, from " extraction well ", with the flow velocity of 0.2mL/min, extracting is carried out to stabilisation nano zero valence iron suspension, and with the flow velocity of 0.2mL/min, stabilisation nano zero valence iron suspension is injected in " Injection Well ", injection length is 1.5h, again suspend 2h, repeat to inject circulation, suspend, to reinject circulation, pause step again, until during 24h, thorough stopping is injected, utilize circulating pump to implement batch (-type) waterpower and promote circulation, in soil certain depth region, form circulation flow field, make the stabilisation nano zero valence iron suspension of injection be no longer stop inactive state, but be in " intermittent flow is dynamic ".
(4) the reduction liquid extracted from " extraction well " is put into fluid storage tank, and inject reduction liquid to " Injection Well ", and fluid storage tank keeps starvation, simultaneously, thermostatic process is carried out with heating rod and temperature controller to reducing liquid in fluid storage tank, add appropriate acid-base buffer, regulating the acid-base value of reduction liquid to remain on pH value is 6.5, to maintain the acid-base condition of reduction reaction simultaneously.
Described acid-base buffer is the hydrochloric acid of 0.8mol/L and the sodium acid carbonate mixed liquor of 0.2mol/L.
Embodiment 2
Heavy metal technique in a kind of circular flow field intensity of the present embodiment Nanoscale Iron rehabilitating soil, comprises the following steps:
(1) first take the sodium carboxymethylcellulose 0.02L that mass percent concentration is 1.0%, be dissolved in distilled water, be placed in the container of starvation, heat under constant temperature vibration condition, obtained carboxymethylcellulose sodium solution; Then in carboxymethylcellulose sodium solution, pass into high pure nitrogen, high pure nitrogen flow velocity is 80mL/min, and the time is 25min, is the FeSO of 0.02mol/L by pre-configured concentration
47H
2o solution adds and passes in the carboxymethylcellulose sodium solution of high pure nitrogen, under high pure nitrogen protection, fully stir 30min under constant temperature, is the NaBH of 0.05mol/L in whipping process by concentration
4solution also dropwise and at the uniform velocity instill in the container of starvation, continues at the uniform velocity isothermal vibration 25min, and obtained stabilisation nano zero valence iron suspension, the concentration of the obtained Fe contained by stabilisation nano zero valence iron suspension is 0.30g/L, wherein FeSO
47H
2o solution and NaBH
4the addition of solution calculates according to the content of beary metal in soil to be repaired;
(2) choosing is the chromium slag contaminated site soil of 0.2g/kg containing Cr (VI) concentration, select at the soil region that need administer and add section, bore at selected cross section place place and dig transverse direction and longitudinal separation is 2.0m, diameter be 100mm add well, that is arranged by odd number adds well as " Injection Well ", even rows add well as " extraction well ", and form " Injection Well " in a row form spaced with " extraction well ", the degree of depth of " Injection Well " and " extraction well " is as the criterion to reach bottom the soil horizon that need administer simultaneously, perforation floral tube is preset in " Injection Well " with " extraction well ", and floral tube diameter is 95mm, penetration hole diameter is 10mm, pitch of holes is 40mm,
(3) with the stabilisation nano zero valence iron suspension that step (1) obtains by circulating pump, inject feed tube, then " Injection Well " is entered with " extraction well ", inject flow control at 0.5mL/min, injection length is 4h, complete rear time-out 3h to be implanted, from " extraction well ", with the flow velocity of 0.3mL/min, extracting is carried out to stabilisation nano zero valence iron suspension, and with the flow velocity of 0.3mL/min, stabilisation nano zero valence iron suspension is injected in " Injection Well ", injection length is 2h, again suspend 3h, repeat to inject circulation, suspend, to reinject circulation, pause step again, until during 24h, thorough stopping is injected, utilize circulating pump to implement batch (-type) waterpower and promote circulation, in soil certain depth region, form circulation flow field, make the stabilisation nano zero valence iron suspension of injection be no longer stop inactive state, but be in " intermittent flow is dynamic ".
(4) the reduction liquid extracted from " extraction well " is put into fluid storage tank, and inject reduction liquid to " Injection Well ", and fluid storage tank keeps starvation, simultaneously, thermostatic process is carried out with heating rod and temperature controller to reducing liquid in fluid storage tank, add appropriate acid-base buffer, regulating the acid-base value of reduction liquid to remain on pH value is 7.0, to maintain the acid-base condition of reduction reaction simultaneously.
Described acid-base buffer is the hydrochloric acid of 1.0mol/L and the sodium acid carbonate mixed liquor of 0.5mol/L.
Embodiment 3
Heavy metal technique in a kind of circular flow field intensity of the present embodiment Nanoscale Iron rehabilitating soil, comprises the following steps:
(1) first take the sodium carboxymethylcellulose 0.015L that mass percent concentration is 0.9%, be dissolved in distilled water, be placed in the container of starvation, heat under constant temperature vibration condition, obtained carboxymethylcellulose sodium solution; Then in carboxymethylcellulose sodium solution, pass into high pure nitrogen, high pure nitrogen flow velocity is 70mL/min, and the time is 23min, is the FeSO of 0.02mol/L by pre-configured concentration
47H
2o solution adds and passes in the carboxymethylcellulose sodium solution of high pure nitrogen, under high pure nitrogen protection, fully stir 25min under constant temperature, is the NaBH of 0.04mol/L in whipping process by concentration
4solution also dropwise and at the uniform velocity instill in the container of starvation, continues at the uniform velocity isothermal vibration 20min, and obtained stabilisation nano zero valence iron suspension, the concentration of the obtained Fe contained by stabilisation nano zero valence iron suspension is 0.20g/L, wherein FeSO
47H
2o solution and NaBH
4the addition of solution calculates according to the content of beary metal in soil to be repaired;
(2) choosing is the chromium slag contaminated site soil of 0.15g/kg containing Cr (VI) concentration, select at the soil region that need administer and add section, bore at selected cross section place place and dig transverse direction and longitudinal separation is 1.8m, diameter be 80mm add well, that is arranged by odd number adds well as " Injection Well ", even rows add well as " extraction well ", and form " Injection Well " in a row form spaced with " extraction well ", the degree of depth of " Injection Well " and " extraction well " is as the criterion to reach bottom the soil horizon that need administer simultaneously, perforation floral tube is preset in " Injection Well " with " extraction well ", and floral tube diameter is 80mm, penetration hole diameter is 9mm, pitch of holes is 35mm,
(3) with the stabilisation nano zero valence iron suspension that step (1) obtains by circulating pump, inject feed tube, then " Injection Well " is entered with " extraction well ", inject flow control at 0.3mL/min, injection length is 3h, complete rear time-out 2.5h to be implanted, from " extraction well ", with the flow velocity of 0.25mL/min, extracting is carried out to stabilisation nano zero valence iron suspension, and with the flow velocity of 0.25mL/min, stabilisation nano zero valence iron suspension is injected in " Injection Well ", injection length is 1.8h, again suspend 2.5h, repeat to inject circulation, suspend, to reinject circulation, pause step again, until during 24h, thorough stopping is injected, utilize circulating pump to implement batch (-type) waterpower and promote circulation, in soil certain depth region, form circulation flow field, make the stabilisation nano zero valence iron suspension of injection be no longer stop inactive state, but be in " intermittent flow is dynamic ".
(4) the reduction liquid extracted from " extraction well " is put into fluid storage tank, and inject reduction liquid to " Injection Well ", and fluid storage tank keeps starvation, simultaneously, thermostatic process is carried out with heating rod and temperature controller to reducing liquid in fluid storage tank, add appropriate acid-base buffer, regulating the acid-base value of reduction liquid to remain on pH value is 6.8, to maintain the acid-base condition of reduction reaction simultaneously.
Described acid-base buffer is the hydrochloric acid of 0.9mol/L and the sodium acid carbonate mixed liquor of 0.4mol/L.
By the soil after this PROCESS FOR TREATMENT, after leaving standstill 5d, detect Cr (VI) content of degree of depth 1.0m place soil, result shows that the removal efficiency of Cr (VI) in the soil in this place is 96.2%.
Claims (2)
1. the heavy metal technique in circular flow field intensity Nanoscale Iron rehabilitating soil, is characterized in that comprising the following steps:
(1) first take sodium carboxymethylcellulose 0.01 ~ 0.02L that mass percent concentration is 0.8 ~ 1.0%, be dissolved in distilled water, be placed in the container of starvation, heat under constant temperature vibration condition, obtained carboxymethylcellulose sodium solution; Then in carboxymethylcellulose sodium solution, pass into high pure nitrogen, high pure nitrogen flow velocity is 50 ~ 80mL/min, and the time is 20 ~ 25min, is the FeSO of 0.01 ~ 0.02mol/L by pre-configured concentration
47H
2o solution adds and passes in the carboxymethylcellulose sodium solution of high pure nitrogen, under high pure nitrogen protection, fully stir 20 ~ 30min under constant temperature, is the NaBH of 0.03 ~ 0.05mol/L in whipping process by concentration
4solution also dropwise and at the uniform velocity instill in the container of starvation, continues at the uniform velocity isothermal vibration 15 ~ 25min, and obtained stabilisation nano zero valence iron suspension, the concentration of the obtained Fe contained by stabilisation nano zero valence iron suspension is 0.10 ~ 0.30g/L, wherein FeSO
47H
2o solution and NaBH
4the addition of solution calculates according to the content of beary metal in soil to be repaired;
(2) section is added the soil region that need administer is selected, bore at selected cross section place place and dig transverse direction and longitudinal separation is 1.5 ~ 2.0m, diameter be 60 ~ 100mm add well, that is arranged by odd number adds well as " Injection Well ", even rows add well as " extraction well ", and form " Injection Well " in a row form spaced with " extraction well ", the degree of depth of " Injection Well " and " extraction well " is as the criterion to reach bottom the soil horizon that need administer simultaneously, perforation floral tube is preset in " Injection Well " with " extraction well ", and floral tube diameter is 55 ~ 95mm, penetration hole diameter is 8 ~ 10mm, pitch of holes is 30 ~ 40mm,
(3) with the stabilisation nano zero valence iron suspension that step (1) obtains by circulating pump, inject feed tube, then " Injection Well " is entered with " extraction well ", inject flow control at 0.2 ~ 0.5mL/min, injection length is 2 ~ 4h, complete rear time-out 2 ~ 3h to be implanted, from " extraction well ", with the flow velocity of 0.2 ~ 0.3mL/min, extracting is carried out to stabilisation nano zero valence iron suspension, and with the flow velocity of 0.2 ~ 0.3mL/min, stabilisation nano zero valence iron suspension is injected in " Injection Well ", injection length is 1.5 ~ 2h, again suspend 2 ~ 3h, repeat to inject circulation, suspend, to reinject circulation, pause step again, until during 24h, stop injecting,
(4) the reduction liquid extracted from " extraction well " is put into fluid storage tank, and inject reduction liquid to " Injection Well ", and fluid storage tank keeps starvation, simultaneously, thermostatic process is carried out with heating rod and temperature controller to reducing liquid in fluid storage tank, add appropriate acid-base buffer, regulating the acid-base value of reduction liquid to remain on pH value is 6.5 ~ 7.0 simultaneously.
2. the heavy metal technique in a kind of circular flow field intensity Nanoscale Iron rehabilitating soil according to claim 1, is characterized in that: described acid-base buffer is the hydrochloric acid of 0.8 ~ 1.0mol/L and the sodium acid carbonate mixed liquor of 0.2 ~ 0.5mol/L.
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| CN106984640A (en) * | 2017-05-08 | 2017-07-28 | 湖南大学 | The method of nano zero valence iron restoration of soil polluted by heavy metal |
| CN108246794A (en) * | 2018-03-01 | 2018-07-06 | 环境保护部南京环境科学研究所 | Improve method of the nano zero valence iron in heavy-metal composite pollution soil stabilization efficiency |
| CN108723073A (en) * | 2018-04-20 | 2018-11-02 | 华南理工大学 | A kind of method of modified Nano Zero-valent Iron collaboration microorganism remediation heavy-metal contaminated soil |
| CN109351767A (en) * | 2018-10-19 | 2019-02-19 | 华南理工大学 | A kind of method of superfine iron powder collaboration microorganism remediation chromium-polluted soil |
| CN110076192B (en) * | 2019-05-31 | 2022-02-15 | 华南理工大学 | In-situ remediation method for heavy metal contaminated soil |
| CN111229812B (en) * | 2020-02-11 | 2021-01-19 | 生态环境部南京环境科学研究所 | Modified nano zero-valent iron and application thereof in remediation of heavy metal contaminated soil |
| CN115215422B (en) * | 2022-05-19 | 2023-05-09 | 成都理工大学 | Method for repairing organic pollution of underground water by in-situ reaction zone |
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