CN105798058B - A method of repairing six six six contaminated soil - Google Patents
A method of repairing six six six contaminated soil Download PDFInfo
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- CN105798058B CN105798058B CN201610365337.1A CN201610365337A CN105798058B CN 105798058 B CN105798058 B CN 105798058B CN 201610365337 A CN201610365337 A CN 201610365337A CN 105798058 B CN105798058 B CN 105798058B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
A method of repairing six six six contaminated soil, comprising: electrolytic salt, beta-cyclodextrin and pure water is added in contaminated soil, is uniformly mixed；The pH value of gained soil is adjusted to 5.07；Gained soil is placed in the electronic room of an electric device and carries out electro reclamation；FeSO of the electronic room in the useful net constraint of insertion at anode 6cm4·7H2The plate of O Crystallization is as permeable reactive barrier；Start the electric device, the time of electro reclamation soil is 190-200h.Recovery technique of the invention is not required to excavate, in-situ immobilization；It is selectively low to soil, it is widely applicable；Easy to operate, expense is lower；Remediation efficiency is high；Low cost, soil remediation efficiently, safe may be implemented using the method for the present invention.
Description
Technical field
The invention belongs to Environmental Chemistry technical fields, and in particular to the improvement and reparation of contaminated soil, especially one kind are repaired
The method of multiple six six six contaminated soil.
Background technique
Six six six (HCHs, chemical formula C6H6Cl6) also known as hexachlorocyclohexanes, it is one kind of organochlorine insecticide, due to
Chemistry, physics and biological stability with height.Six six six is used as typical case POPs(persistence organic pollutant), in
It is put within 2011 " Convention of Stockholm about persistence organic pollutant " control list.It is counted according to historical data,
For six six six when stopping production nineteen eighty-three, the cumulant in China has reached 4,900,000 t, accounts for the 33% of produced worldwide total amount.And 20
The fifties in century, China's six six six added up to use about 400,000 t to during nineteen eighty-three.In history Henan, Hebei, Shandong, Sichuan,
The most areas such as Hunan, Guangzhou once carried out centralized production to six six six, and use scope is even more throughout the country.
Six six six can cause human central nervous system's excitement, spasm, respiratory failure, lung swollen and dermatitis acute reaction etc.
Toxic reaction.Investigation shows that plant area of six six six manufacturing enterprise soil is contaminated in varying degrees.It is developed and used to plant area
It is easy to occurrence injury event in the process.Such as, acute poisoning event has occurred in personnel when Foundation of Beijing Metro Line 5 is built within 2004.
Therefore, it is very urgent that six six six contaminated soil method is effectively repaired in exploitation.
Common six six six contaminated soil remediation technology includes peripheral doses, chemical remediation and bioremediation technology at present,
Such as soil removal and replacement/soil improvement by importing soil from other places, chemical leaching recovery technique, thermal desorption recovery technique and microorganism remediation.But these restorative procedures one
As that there are site requirements is higher, costly, the period is long, low efficiency, the disadvantages of cannot administering at all, in case history
Gradually replaced emerging recovery technique.In recent years, electric repairing technique is studied to have obtained further development, domestic and foreign scholars' needle
Some Organic Pollutants (such as bisphenol-A, dimethylbenzene, pyrene and phenol) are tested, the results showed that, in certain reaction
Between, under the conditions of voltage gradient, w (electrolyte) and pH, organic pollutant can be enriched with by electrodynamic action to a certain region, be had
It is removed conducive to concentrating.In addition, organic contaminants in soil also can be anti-by electrochemical action generation redox near electrode
It answers, to be degraded.But due to the features such as six six six dissolubility is poor, weak and polarity of freeing ability is weak, lead to its degradation efficiency
It is very low.
Some advantage and disadvantage are individually present in electrokinetic technique and chemical technology in view of six six six contaminated soil, need to join the two
Cooperation is used.But the suitable associative mechanism of electric driving method and Fenton (Fenton) method how is specifically found, including suitably add
Agent and its ratio etc. enable two technologies effectively to play synergistic effect, this is always the technical problem of this field, lacks and specifically may be used
Capable technical solution.
Summary of the invention
In view of this, it is a primary object of the present invention to make up the deficiency of the recovery technique of existing six six six contaminated soil,
A kind of electric repair method of six six six contaminated soil is provided.
To achieve the goals above, the present invention provides a kind of methods for repairing six six six contaminated soil, including following step
It is rapid:
Step 1, electrolytic salt, beta-cyclodextrin and pure water is added in contaminated soil, is uniformly mixed；Wherein, it is electrolysed
Matter salt dosage is that the contaminated soil of every hectogram adds 2-6g, preferably 2-4g；Beta-cyclodextrin dosage is contaminated for every hectogram
Soil adds 2-6g beta-cyclodextrin, preferably 2-4g；Pure water dosage is that the contaminated soil of every hectogram adds 25-50ml, excellent
It is selected as 30-45ml；
Step 2, the pH value of step 1 gained soil is adjusted to 5.00-5.10；
Step 3, step 2 gained soil is placed in the electronic room of an electric device and carries out electro reclamation；The electronic dress
It sets including cathode and anode, the cathode and anode are located at the two sides of the electronic room；It is set at anode 6.0-6.30cm
Set the FeSO with net constraint4·7H2The plate of O Crystallization is as permeable reactive barrier；
Step 4, start the electric device, the time of electro reclamation soil is 190-200h.
Compared with the existing technology, the present invention has the following beneficial effects:
(1) present invention is effective, feasible, electric driving method using electronic-Fenton process joint reparation six six six contaminated soil
Played synergy effect with Fenton process, 50% or more reached to the degradation rate of six six six in soil, be it is a kind of efficiently,
Safety, the method for rehabilitating soil six six six pollution without secondary pollution；In addition, the removal rate of six six six isomers has differences,
β-HCH removal rate highest is that 96.7%, α-HCH takes second place and is then respectively for the removal rate of 79.9%, γ-HCH and δ-HCH
54.8% and 51.7%；
(2) due to the features such as six six six dissolubility is poor, weak and polarity of freeing ability is weak, simple application electric field force, migration
Effect is not obvious；Beta-cyclodextrin enhancing six six six polarity is added in the present invention in the soil, has well solved this problem；
(3) electronic-Fenton combined remediation technology of the invention is not required to excavate, in-situ immobilization；It is selectively low to soil, it is applicable in
It is wide；Easy to operate, expense is lower；Remediation efficiency is high；Low cost, soil efficiently, safe may be implemented using the method for the present invention
Earth reparation.
Detailed description of the invention
Fig. 1 is the floor map of the electronic generating device used in electronic-Fenton process combined remediation technology of the invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The invention discloses a kind of methods that electronic-Fenton process joint repairs six six six contaminated soil, comprising the following steps:
(1) electrolytic salt, beta-cyclodextrin and pure water is successively added to be uniformly mixed with six six six contaminated soil；Electrolytic salt
(by taking NaCl as an example) dosage is that every hectogram soil adds 2-6g, preferably 2-4g；Beta-cyclodextrin dosage is every hectogram soil
Add 2-6g beta-cyclodextrin, preferably 2-4g；Pure water dosage is that every hectogram soil adds 25-50ml pure water, preferably
30-45ml；
(2) pH value for the soil that step (1) obtains is adjusted to 5.00-5.10, preferably 5.07；
(3) soil for obtaining step (2) is stood for 24 hours；
(4) soil that step (3) obtains is placed in an electric device as shown in Figure 1 and carries out electro reclamation, this is electronic
Device includes the cathode and anode being respectively communicated with power cathode and anode, and electrode material can for example use graphite rod, blue
Place contaminated soil to be repaired in region；Catholyte is NaCl in the electric device, and anolyte is hydrogen peroxide；?
The FeSO of setting net constraint at anode 6.0-6.30cm, preferably 6cm4·7H2The plate of O Crystallization is as permeable
Reaction wall.In the electric device, for carbon-point as working electrode, for example long 30cm of reaction chamber, width 10cm, high 15cm can bases
Need of work adjustment.Yin-yang the two poles of the earth are isolated with permeable reactive barrier, prevent the soil in reaction chamber from leaking to the two poles of the earth.
Preferably, the electric device can with in-situ construction, such as formed by way of cathode well, anode well cathode and
Anode is inserted into FeSO into soil layer4·7H2The plate of O Crystallization is as permeable reactive barrier.
Preferably, the operating voltage of the electric device be 100V-110V, voltage gradient 2.9-3.5V/cm, preferably
3V/cm。
Preferably, the time of electro reclamation soil is 190-200h, preferably 192h.
Wherein, it is respectively further comprised to six six six contaminated soil according to national standards before step (1) and after step (4)
The step of gas-chromatography GC analysis detection of the progress sample pretreatment of GB/T14550-2003 method and six six six.
The present invention is described in more detail combined with specific embodiments below.Material employed in following embodiments, examination
Agent etc., unless otherwise specified, for the reagent and material commercially obtained；Used test method is such as without special theory
It is bright, it is conventional method.
Embodiment 1: the reparation that different voltages gradient pollutes soil six six six
It is as shown in table 1 for the six six six background value of examination soil.
Different voltage gradients, respectively 1,1.5,2,2.5, totally 4 groups of 3V/cm are set.Every group of energization 192h, if three weights
It is multiple.The gas that GB/T14550-2003 method according to national standards carries out sample pretreatment and six six six is distinguished before repairing and after repairing
Phase chromatography (GC) analysis detection.
The result shows that: six six six throughout manage in degradation effect increase with the enhancing of voltage gradient.But it considers
In terms of cost and practical operation, it is optimal for selecting the voltage gradient of 3V/cm.
Embodiment 2: the reparation that energization different time pollutes soil six six six
It is as shown in table 1 for the six six six background value of examination soil.
Different conduction time is set, respectively 12h, for 24 hours, totally five groups of 48h, 96h, 192h.Every group of voltage gradient is 3V/
Cm, if three repetitions.GB/T14550-2003 method carries out sample pretreatment according to national standards respectively before repairing and after repairing
With gas-chromatography (GC) analysis detection of six six six.
The result shows that: the treatment effect of six six six enhances with the increase of electronic time, but increases after being switched on 192h
Treatment effect obviously slow down, for cost consideration, be not further added by conduction time.
Embodiment 3: electronic, Fenton, electronic-Fenton joint influence to the pollution of rehabilitating soil six six six respectively are studied.
It is as shown in table 1 for the six six six background value of examination soil.
The w of each sampled point of table 10Value
Note: w0The w for the sampled point that (Φ) table is not Φ away from cathode standardization distance0Mean value
A. electronic group: pretreated soil being put into electrolysis unit as shown in figure 1, catholyte and anolyte are NaCl molten
Liquid is not provided with permeable reactive barrier, is tested under the conditions of constant DC voltage 3V/cm, 192h.Experiment remains original soil
PH value 5.07, control moisture content is 35%, w (electrolyte) and w (cyclodextrin) is 2%.Electrode plug is plugged, power supply is opened and opens
It closes, starts electronic experiment.
B. Fenton group: accurately weighing the contaminated soil that 200g has been prepared with electronic analytical balance first, and triangular flask is added
In.And catalyst and H are sequentially added thereto2O2Solution keeps original soil pH, and triangular flask is placed in 25 DEG C, 150r/min perseverance later
It vibrates, and is stirred continuously in tepidarium oscillation case.After a certain period of time, the residual volume of HCHs in soil is measured by sampling in reaction.Using
Catalyst amounts w (FeSO4·7H2O crystal) it is 5%, H2O2Concentration ρ (H2O2) it is that 20g/mL is tested.Every 10 minutes
HCHs in contaminated soil is measured, until removal effect is stablized.
C. electronic-Fenton joint group: this experiment is in the FeSO close to excessive addition at anode 6cm4·7H2O crystal, is used in combination
Web materials are fixed, and as permeable reactive barrier, and 30% hydrogen peroxide are added in anolyte.Insert electrodes into cathode/
In anolyte (cathode sodium chloride makees electrolyte, and anode hydrogen peroxide makees electrolyte), in constant DC voltage 3V/cm, 192h item
It is tested under part.Experiment remains original soil pH value 5.07, and control moisture content is 35%, w (electrolyte) and w (cyclodextrin) is equal
It is 2%.Electrode plug is plugged, is turned on the power switch, electronic experiment is started.
The result shows that: simple electrokinetic process is unobvious to degraded hexachloro cyclohexane.Simple Fenton processing, β-HCH removal rate
Highest, be 96.7%, α-HCH take second place for the removal rate of 79.9%, γ-HCH and δ-HCH then be respectively 54.8% and 51.7%.
And electronic-Fenton Combined Treatment is to the removal efficiency highest of β-HCH, is 76.1%, to the removal efficiency of α-HCH take second place for
74.8%, the removal rate to γ-HCH, δ-HCH is respectively 52.8% and 47.8%.Its removal efficiency is slightly below independent Fenton
Oxidation, this is pre- interim in experiment.It is repaired due to electronic-Fenton joint and is substantially carried out in-situ immobilization, it is not necessary to carried out soil big
Scale excavates transfer, therefore considers its economical and practical level, and repairing effect is more excellent.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (12)
1. a kind of method for repairing six six six contaminated soil, which comprises the following steps:
Step 1, electrolytic salt, beta-cyclodextrin and pure water is added in contaminated soil, is uniformly mixed；Wherein, electrolytic salt
Dosage is that the contaminated soil of every hectogram adds 2-6g；Beta-cyclodextrin dosage is that the contaminated soil of every hectogram adds 2-6g β-
Cyclodextrin；Pure water dosage is that the contaminated soil of every hectogram adds 25-50ml；
Step 2, the pH value of step 1 gained soil is adjusted to 5.00-5.10；
Step 3, step 2 gained soil is placed in the electronic room of an electric device and carries out electro reclamation；The electric device packet
Cathode and anode are included, the cathode and anode are located at the two sides of the electronic room；The electrolyte of the cathode is sodium chloride solution,
The electrolyte of the anode is hydrogen peroxide；In the setting FeSO of net constraint at anode 6.0-6.30cm4·7H2O crystal
The plate of formation is as permeable reactive barrier；
Step 4, start the electric device, the time of electro reclamation soil is 190-200h.
2. the method according to claim 1, wherein the electrolytic salt is sodium chloride.
3. the method according to claim 1, wherein electrolytic salt dosage is contaminated for every hectogram in step 1
Soil adds 2-4g.
4. the method according to claim 1, wherein beta-cyclodextrin dosage is contaminated for every hectogram in step 1
Soil adds 2-4g beta-cyclodextrin.
5. the method according to claim 1, wherein pure water dosage is the contaminated soil of every hectogram in step 1
Earth adds 30-45ml.
6. the method according to claim 1, wherein before step 3 further including standing step 2 gained soil
For 24 hours the step of.
7. the method according to claim 1, wherein the electrode material of cathode described in step 3 and anode is adopted
Use graphite rod.
8. the method according to claim 1, wherein the long 30cm in electronic room described in step 3, width 10cm, height
15cm。
9. the method according to claim 1, wherein the operating voltage of electric device described in step 4 is 100V-
110V。
10. the method according to claim 1, wherein in electric device described in step 4 power supply voltage gradient
For 2.9-3.5V/cm.
11. the method according to claim 1, wherein the soil of electric device electro reclamation described in step 4 when
Between be 192h.
12. the method according to claim 1, wherein respectively further comprising before step 1 and after step 4 to institute
State contaminated soil according to national standards GB/T14550-2003 method carry out sample pretreatment and six six six gas-chromatography GC
The step of analysis detection.
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| CN106631485A (en) * | 2016-12-28 | 2017-05-10 | 贵州大学 | Fertilizer for remedying pollution caused by hexachlorocyclohexane |
| CN106986501B (en) * | 2017-05-08 | 2023-02-03 | 中国科学院水生生物研究所 | Method and device for treating sewage by coupling electric osmosis reaction wall and constructed wetland |
| CN110180886B (en) * | 2019-07-05 | 2021-03-02 | 河南科技大学 | Device and method for in-situ remediation of fluorine-contaminated soil |
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| CN1827248A (en) * | 2006-04-12 | 2006-09-06 | 华中科技大学 | Process for repairing organic material contaminated soil |
| JP2010240636A (en) * | 2009-03-19 | 2010-10-28 | Dowa Eco-System Co Ltd | Decomposer for organohalogen compound, method for producing the same and method for purifying soil or water |
| CN103286119B (en) * | 2013-06-07 | 2014-10-15 | 华北电力大学 | Device and method for restoring chlorobenzene-type organism polluted soil and underground water |
| RU2540551C2 (en) * | 2013-06-26 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Государственный университет-учебно-научно-производственный комплекс" (ФГБОУ ВПО "Госуниверситет-УНПК") | Method of destruction of isomers of organochlorine pesticide of hexachlorocyclohexane in soil |
| CN103316908B (en) * | 2013-07-05 | 2015-02-25 | 华北电力大学 | Device and method for restoring soil polluted by polychlorinated biphenyl |
| CN103722006B (en) * | 2014-01-09 | 2016-03-02 | 环境保护部南京环境科学研究所 | A kind of organochlorine pesticide pollution soil synergy elution system |
| CN104624622A (en) * | 2014-12-31 | 2015-05-20 | 中国科学院沈阳应用生态研究所 | Renovating preparation for improving electric-microbial remediation of organic substance contaminated soil and using method for renovating preparation |
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