CN109909281A - It is a kind of to synchronize medicament and method fixed and that cut down trichloro ethylene in soil and/or underground water - Google Patents
It is a kind of to synchronize medicament and method fixed and that cut down trichloro ethylene in soil and/or underground water Download PDFInfo
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- CN109909281A CN109909281A CN201910195313.XA CN201910195313A CN109909281A CN 109909281 A CN109909281 A CN 109909281A CN 201910195313 A CN201910195313 A CN 201910195313A CN 109909281 A CN109909281 A CN 109909281A
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Abstract
Medicament and method fixed and that cut down trichloro ethylene in soil and/or underground water are synchronized the invention discloses a kind of.The medicament is cooperated under specific proportion using bentonite, persulfate and water three, while bentonite uses the sodium bentonite of particular characteristic, can effectively activate persulfate to generate the SO of more strong oxidizing properties using the sodium bentonite of the particular characteristic4 ·‑And OH does not generate the stronger dechlorination product of the toxicity such as vinylidene chloride, 1,2-dichloroethene or vinyl chloride using its exhaustive oxidation trichloro ethylene, to improve TCE removal rate in the pollution source area DNAPL.Meanwhile the sodium bentonite of the particular characteristic can maintain reaction system pH to stablize during removing trichloro ethylene, so be not required to additionally add base reagent during the reaction and be not required to adjust pH value.After tested, TCE removal rate reaches in 51%~56%, 64 day in 8 days and reaches 93%~100%.
Description
Technical field
The invention belongs to soil and Groundwater Contamination Risk control and improvement recovery technique fields, and in particular to a kind of synchronization
Medicament and method fixed and that cut down trichloro ethylene in soil and/or underground water, in particular to a kind of bentonite couple persulfuric acid
Salt synchronize it is fixed cut down soil and/or underground water heavy nonaqueous phase liquid (dense non aqueous phase liquid,
DNAPL) in pollution source area trichloro ethylene medicament and method.
Background technique
Trichloro ethylene (trichloroethylene, TCE) is generally existing in soil and groundwater in world wide waves
One of hair property chlorinatedorganic, pollution has become global environment and health problem.According to incompletely statistics, China,
High concentration TCE is detected in the soil and groundwater of the country such as Britain, Japan, the U.S., Belgium.TCE in soil and groundwater
Be mainly derived from organic solvent, dry cleaning agent and anesthetic holding vessel leakage or be not effectively addressed and the waste liquid that discharges.
TCE was classified as " priority acccess control compound " by the U.S. early in 1976, was also classified as Chinese environmental priority monitoring by China
With control pollutant, there is potential carcinogenic, teratogenesis, mutagenesis characteristic.It is a kind of non-aqueous phase of the heavy that density ratio water is big
Liquid (dense non aqueous phase liquid, DNAPL), solubility very little (1100mg/L) in water compares water
Density is big, and viscosity is low.TCE migration velocity in soil and aeration zone is fast, is trapped in media voids with drops, and into
Water-bearing layer bottom can be then trapped in by entering underground water part, form the pollution source area DNAPL, and as Groundwater movement gradually dissolves
Into water, secondary pollution is caused.TCE can become continuous, lasting pollution source of groundwater in the pollution source area DNAPL.
Currently, the risk management and control in situ of TCE is mainly wrapped with recovery technique is administered in the pollution source area soil and groundwater DNAPL
Include Barrier Technology and electronation technology etc..Wherein, it is non-to rely primarily on clay, bentonite, cement, mixed flyash etc. for Barrier Technology
Permeable material builds barrier wall and blocks the diffusion of pollution sources migrated downstream.Barrier Technology is only capable of cutting route of exposure, and limitation is dirty
Contaminate plumage migration, but cannot reduce pollutant concentration and exist lead to pollutant risk of leakage.In most cases, Barrier Technology is
It is used as a kind of provisional control method at underground water pollution control initial stage.
Electronation technology relies primarily on Zero-valent Iron as electron donor and provides electronics, TCE as electron acceptor receiving electricity
Hydrogenolysis or dechlorination occur for the principle of son.Granular iron column experiments result of study shows at initial operating stage (≤20 pore volumes), zero
Valence iron can completely remove TCE, but Zero-valent Iron is passivated when operation to 90 pore volumes, and TCE removal rate is reduced to 60%,
Supervene the chloros by-products such as cis- -1,2- dichloroethylene, vinyl chloride.In addition, granular iron easily is oxidized by oxygen to form FeOOH
Or Fe (OH)3, hinder pollutant to be in contact with it and block its gap, to reduce permeability and conductivity etc..
In practical applications, above-mentioned technology cuts down soil and groundwater heavy nonaqueous phase liquid (dense non fixed
Aqueous phase liquid, DNAPL) there are pH variations during trichloro ethylene in pollution source area greatly, TCE removal rate it is low with
And it is also easy to produce 1,1- dichloroethylene, 1,2- dichloroethylene or vinyl chloride, barrier wall infiltration coefficient and length of service technical requirements height
Defect.
Summary of the invention
For this purpose, to be solved by this invention is that the prior art is dirty in fixed reduction soil and groundwater heavy nonaqueous phase liquid
Contaminating trichloro ethylene in source region, there are pH to change greatly in the process, and TCE removal rate is low and is also easy to produce vinylidene chloride, 1,2- dichloro
Ethylene or vinyl chloride, barrier wall infiltration coefficient and the high defect of length of service technical requirements, so provide it is a kind of synchronize it is fixed and
Cut down the medicament and method of trichloro ethylene in soil and/or underground water.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
It is provided by the present invention to synchronize medicament that is fixed and cutting down trichloro ethylene in soil and/or underground water, including swelling
The mass ratio of soil, persulfate and water, the bentonite and persulfate is 3000~5000:300~500, the bentonite
Mass ratio with water is 1~2:40~60；
The bentonite is sodium bentonite, Na in the sodium bentonite+Content is 2wt%~4wt%, total organic carbon
Content is 10~15mg/L, and pH is 10.0~11.0, and partial size is 75~180 μm.
Further, the mass ratio of the bentonite and persulfate is 3800~4200:350~400, the bentonite
Mass ratio with water is 1~2:45~55；
The bentonite is sodium bentonite, Na in the sodium bentonite+Content is 2.5wt%~3wt%, total organic
Carbon content is 13~14mg/L, and pH is 10.3~10.8, and partial size is 120~150 μm.
Further, the persulfate is potassium peroxydisulfate and/or sodium peroxydisulfate, the purity of the persulfate >=
98wt%.
Further, the persulfate is potassium peroxydisulfate and sodium peroxydisulfate, the matter of the potassium peroxydisulfate and sodium peroxydisulfate
Amount is than being 1:(4-5).
In addition, it is necessary to which explanation, the pH test method of sodium bentonite are as follows: being added into sodium bentonite ultrapure
Water, and the mass ratio for controlling sodium bentonite and ultrapure water is that 1:50 measures the pH value of water after blender stirring surpasses 24 hours,
The pH value is the pH of sodium bentonite.
Above-mentioned medicament the preparation method comprises the following steps: bentonite, persulfate and water are weighed in mass ratio, and be stirred at room temperature
Uniformly, so that bentonite is in suspended state, medicament is made.
In addition, the present invention also provides synchronize three chloroethenes in fixed and reduction soil and/or underground water using above-mentioned medicament
The method of alkene, includes the following steps:
S1, bentonite is mixed with water, mud is made；
S2, using cofferdam or high-pressure injection mode, by the slurry prime in step S1 to the pollution source area DNAPL surrounding soil
In the aqueous medium of underground, forms vertical divider wall and/or horizontal barrier wall, the diffusion mobility of blocking dna PL pollution sources fix three
Vinyl chloride；
S3, the medicament is injected into the pollution source area DNAPL, trichloro ethylene therein of degrading.
Further, in step S1, the mass ratio of bentonite and water is 1~2:40~60.
Further, in step S2, infiltration coefficient≤1 × 10 of the vertical divider wall-7Cm/s, 9~19cm of thickness；
Infiltration coefficient≤1 × 10 of the horizontal barrier wall-7Cm/s, 9~19cm of thickness.
Further, in step S3, the matter of persulfate and trichloro ethylene in the pollution source area DNAPL in the medicament
Amount is than being 300~500:1~5.
Further, in step S2, as the pollution source area the DNAPL buried depth < 10m, implemented by the way of cofferdam；Or,
In step S2, when the pollution source area DNAPL buried depth is 10~30m, by the way of high-pressure injection.
Further, by the aeration zone around the slurry prime in step S1 to the pollution source area DNAPL, in aeration zone and
Vertical divider wall and horizontal barrier wall are formed around the pollution source area DNAPL；Or,
By the slurry prime in step S1 into the pollution source area DNAPL downstream water-bearing layer, vertical divider wall is formed.
Compared with prior art, the invention has the following beneficial effects:
(1) provided by the present invention to synchronize medicament that is fixed and cutting down trichloro ethylene in soil and/or underground water, use is swollen
Profit soil, persulfate and water three cooperate under specific proportion, while bentonite uses the sodium bentonite of particular characteristic, utilize
The sodium bentonite of the particular characteristic can effectively activate persulfate to generate the SO of more strong oxidizing properties4 ·-And OH, it utilizes
SO4 ·-With OH exhaustive oxidation trichloro ethylene, it is stronger that the toxicity such as vinylidene chloride, 1,2-dichloroethene or vinyl chloride are not generated
Dechlorination product, to improve TCE removal rate in the pollution source area DNAPL.Meanwhile the sodium bentonite of the particular characteristic is removing
Reaction system pH can be maintained to stablize during trichloro ethylene, so be not required to additionally add base reagent during the reaction and be not required to adjust
Save pH value.After tested, TCE removal rate reaches in 8 days reaches 93%~100% in 51%~56%, 64 day, in reaction process
The stronger dechlorination product of the toxicity such as 1,2-dichloroethene and vinyl chloride is not generated, and secondary pollution is small, and Ecological Environment Risk is small, safety
Property it is high, there is significant advantage in the technical and feature of environmental protection.
(2) provided by the present invention to synchronize medicament that is fixed and cutting down trichloro ethylene in soil and/or underground water, using sodium
Base bentonite, and optimize Na in sodium bentonite+Content, total content of organic carbon, pH and partial size can improve the touching of sodium bentonite
Become the performances such as plasticity, dilatancy and caking property, so as to make the effective filling soil of the sodium bentonite, aeration zone and underground water
The gap of medium can finally block the migration and diffusion of trichloro ethylene long-term effectively.
(3) provided by the present invention to synchronize medicament that is fixed and cutting down trichloro ethylene in soil and/or underground water, persulfuric acid
Salt is potassium peroxydisulfate and sodium peroxydisulfate, and the mass ratio of potassium peroxydisulfate and sodium peroxydisulfate is 1:(4-5), pass through different types of over cure
Hydrochlorate is used cooperatively as specific, helps to improve TCE removal rate in the pollution source area DNAPL.
(4) provided by the present invention to synchronize method that is fixed and cutting down trichloro ethylene in soil and/or underground water, it first will be swollen
Profit soil is mixed with water, and mud is made；Cofferdam or high-pressure injection mode are used again, around slurry prime to the pollution source area DNAPL
In soil and groundwater medium, formation vertical divider wall and/or horizontal barrier wall, the diffusion mobility of blocking dna PL pollution sources, Gu
Determine trichloro ethylene；Medicament is finally injected into the pollution source area DNAPL, bentonite is filled in soil and groundwater media voids in medicament
Interior, persulfate is scattered in pollution source area by gravity and capillary phenomenon, forms hyposmosis reaction zone, extends three chloroethenes
Alkene is in the residence time of reaction zone, with complete oxidation degradation trichloro ethylene.
(5) provided by the present invention to synchronize method that is fixed and cutting down trichloro ethylene in soil and/or underground water, pass through by
Bentonite and water are mixed to form mud by extra fine quality ratio, which is suitable for being filled into the pollution source area DNAPL surrounding soil and ground
In lower aqueous medium, vertical divider wall and/or horizontal barrier wall are formed；Pass through preferred vertical barrier wall and/or horizontal barrier wall
Infiltration coefficient and thickness block the migration and diffusion of trichloro ethylene；By limiting persulfate and the pollution source area DNAPL in medicament
The mass ratio of middle trichloro ethylene can improve TCE removal rate in the pollution source area DNAPL.
(6) provided by the present invention to synchronize method that is fixed and cutting down trichloro ethylene in soil and/or underground water, it does not need
Heating, ultraviolet light, transition metal ions and hydrogen peroxide etc. can carry out under normal temperature and pressure, and reaction system is simple, react item
Part is mild, and operation and maintenance management cost is low.Using this method, can be significantly reduced to existing barrier wall thickness and the service time limit
The technical requirements of (at least 10 years), and then reduce barrier wall construction cost.It is especially deep that soil and groundwater may be implemented simultaneously
Layer groundwater pollutant fixation in situ and improvement are repaired and emergency pollution is handled, applied widely.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that bentonite and persulfate are combined synchronous fixation in situ and cut down underground water DNAPL in the embodiment of the present invention
The structural representation and laying state diagram of pollution source area trichloro ethylene；
Fig. 2 is that 4 bentonite of the embodiment of the present invention and persulfate are combined synchronous fixation in situ and cut down soil DNA PL pollution
The structural representation and laying state diagram of source region trichloro ethylene；
It is short with the reaction time that Fig. 3 is TCE removal rate caused by bentonite and persulfate are combined in the embodiment of the present invention
Phase variation diagram；
Fig. 4 is that bentonite and the caused TCE oxidative degradation kinetic linearity of persulfate combination are quasi- in the embodiment of the present invention
Close figure；
It is short with the reaction time that Fig. 5 is reaction system pH caused by bentonite and persulfate are combined in the embodiment of the present invention
Phase variation diagram；
Fig. 6 is that bentonite and persulfate are combined caused TCE removal rate with the length in reaction time in the embodiment of the present invention
Phase variation diagram；
Fig. 7 is that bentonite and persulfate are combined caused reaction system pH with the length in reaction time in the embodiment of the present invention
Phase variation diagram；
Fig. 8 is that bentonite and persulfate are combined caused reaction system Eh with the length in reaction time in the embodiment of the present invention
Phase variation diagram；
Fig. 9 is that bentonite and persulfate are combined caused reaction system S in the embodiment of the present invention2O8 2-Residual quantity is with anti-
Change in long term figure between seasonable；
Figure 10 is bentonitic SEM (5000 times) shape appearance figure in the embodiment of the present invention；
Figure 11 is bentonitic EDS analysis of spectra in the embodiment of the present invention.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Term " bentonite " is the aqueous clay pit using montmorillonite as main mineral constituent in the present invention, and montmorillonite belongs to 2:
1 type crystal structure is pressed from both sides one layer of alumina octahedral by two oxygen-octahedrons and is formed, and main chemical compositions are silica, three oxygen
Change two aluminium and water, also containing the elements such as iron, magnesium, calcium, sodium, potassium, hardness 1~2,2~3g/cm of density3, in it is yellowish green, yellowish-white, grey,
The colors such as white add volume after water to swell several times to 20~30 times.Montmorillonite structure cell formed layer structure there are it is certain sun from
Son, such as Cu2+、Mg2+、Na+、K+.These cations are very unstable with the effect of montmorillonite structure cell, easily exchanged by other cations.
Term " heavy nonaqueous phase liquid (dense non aqueous phase liquid, DNAPL) " in the present invention be
The general name for referring to liquid pollutant all not soluble in water in soil and groundwater and that density ratio water is big, such as coal tar, the wooden pomegranate oil, three
Vinyl chloride and tetrachloro-ethylene have lower solubility and higher interfacial tension.
" trichloro ethylene (trichloroethylene, TCE) is molecular formula C to term in the present invention2HCl3, relative molecular weight
131.39,87.1 DEG C of boiling point, -86 DEG C of fusing point, colourless, smell are insoluble in water, are soluble in like inflammable, the volatile liquid of chloroform
Ethyl alcohol, ether etc. are miscible in most organic solvents, represent one of pollutant for DNAPL.
As long as in addition, the non-structure each other of technical characteristic involved in invention described below different embodiments
It can be combined with each other at conflict.
Embodiment 1
Present embodiments provide a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, the medicine
Agent includes the persulfate and water of the bentonite of 4000g, 384g, and the mass ratio of bentonite and water is 1:50；Wherein, bentonite is
Sodium bentonite, Na in sodium bentonite+Content is 2.6wt%, total content of organic carbon 13.7mg/L, pH 10.5, partial size
It is 150 μm, persulfate is sodium peroxydisulfate；
Bentonitic microscopic sdIBM-2+2q.p.approach such as Figure 10 and Figure 11 in the present embodiment, from Figure 10 it can be seen that: bentonitic surface be not
Regular polygon, smooth, tool corner angle；From Figure 11 it can be seen that: its be mainly made of and contain oxygen, silicon, aluminium a small amount of sodium, potassium, iron,
Calcium, magnesium etc., the oxygen-octahedron for meeting montmorillonite press from both sides the 2:1 type crystal structure of one layer of alumina octahedral composition；
Simulation application environment has by the medicament in the present embodiment applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter bentonite, guarantee that the mass ratio of TCE in bentonite, persulfate and the anaerobism underground water containing TCE in medicament is 4000:
384:2, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE removal rate in the anaerobism underground water containing TCE
After reaching 56%, reaction 64 days, TCE removal rate reaches 100% in the anaerobism underground water containing TCE.
Embodiment 2
Present embodiments provide a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, the medicine
Agent includes the persulfate and water of the bentonite of 4000g, 384g, and the mass ratio of bentonite and water is 1:50；Wherein, bentonite is
Sodium bentonite, Na in sodium bentonite+Content is 2.6wt%, total content of organic carbon 13.7mg/L, pH 10.6, partial size
It is 120 μm, persulfate is potassium peroxydisulfate；
Medicament in the present embodiment is applied in the soil containing TCE of 10mg/kg, concrete application by simulation application environment
Method is as follows: the persulfate in medicament is added in the soil containing TCE of 10mg/kg, add bentonite in medicament and
Water guarantees that the mass ratio of TCE in bentonite, persulfate and the soil containing TCE in medicament is 4000:384:2, in room temperature, often
After reacting 8 days under the conditions of pressure, oscillation (250rpm), TCE removal rate reaches 54% in the anaerobism underground water containing TCE, reaction 64
After it, TCE removal rate reaches 97% in the anaerobism underground water containing TCE.
Embodiment 3
Present embodiments provide a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, the medicine
Agent includes the persulfate and water of the bentonite of 3800g, 400g, and the mass ratio of bentonite and water is 1:55；Wherein, bentonite is
Sodium bentonite, Na in sodium bentonite+Content is 2.5wt%, total content of organic carbon 14mg/L, pH 10.8, and partial size is
130 μm, persulfate is sodium peroxydisulfate；
Simulation application environment has by the medicament in the present embodiment applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter bentonite, guarantee that the mass ratio of TCE in bentonite, persulfate and the anaerobism underground water containing TCE in medicament is 3800:
400:1, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE removal rate in the anaerobism underground water containing TCE
After reaching 55%, reaction 64 days, TCE removal rate reaches 99% in the anaerobism underground water containing TCE.
Embodiment 4
Present embodiments provide a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, the medicine
Agent includes the persulfate and water of the bentonite of 4200g, 350g, and the mass ratio of bentonite and water is 2:45；Wherein, bentonite is
Sodium bentonite, Na in sodium bentonite+Content is 3wt%, total content of organic carbon 13mg/L, pH 10.5, partial size 140
μm, persulfate is potassium peroxydisulfate；
Simulation application environment has by the medicament in the present embodiment applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter bentonite, guarantee that the mass ratio of TCE in bentonite, persulfate and the anaerobism underground water containing TCE in medicament is 4200:
350:5, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE removal rate in the anaerobism underground water containing TCE
After reaching 56.7%, reaction 64 days, TCE removal rate reaches 99.8% in the anaerobism underground water containing TCE.
Embodiment 5
Present embodiments provide a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, the medicine
Agent includes the persulfate and water of the bentonite of 3000g, 500g, and the mass ratio of bentonite and water is 1:60；Wherein, bentonite is
Sodium bentonite, Na in sodium bentonite+Content is 4wt%, and total content of organic carbon 10mg/L, pH 11, partial size is 75 μm,
Persulfate is sodium peroxydisulfate；
Simulation application environment has by the medicament in the present embodiment applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter bentonite, guarantee that the mass ratio of TCE in bentonite, persulfate and the anaerobism underground water containing TCE in medicament is 3000:
500:2, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE removal rate in the anaerobism underground water containing TCE
After reaching 52%, reaction 64 days, TCE removal rate reaches 95% in the anaerobism underground water containing TCE.
Embodiment 6
Present embodiments provide a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, the medicine
Agent includes the persulfate and water of the bentonite of 5000g, 300g, and the mass ratio of bentonite and water is 2:40；Wherein, bentonite is
Sodium bentonite, Na in sodium bentonite+Content is 2wt%, and total content of organic carbon 15mg/L, pH 10, partial size is 180 μ
M, persulfate are potassium peroxydisulfate；
Simulation application environment has by the medicament in the present embodiment applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter bentonite, guarantee that the mass ratio of TCE in bentonite, persulfate and the anaerobism underground water containing TCE in medicament is 5000:
300:2, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE removal rate in the anaerobism underground water containing TCE
After reaching 51%, reaction 64 days, TCE removal rate reaches 93% in the anaerobism underground water containing TCE.
Embodiment 7
A kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water is present embodiments provided, with real
Example 2 is applied, only difference is that: persulfate is the mixture of potassium peroxydisulfate and sodium peroxydisulfate in the present embodiment, wherein mistake
The mass ratio of potassium sulfate and sodium peroxydisulfate is 1:4.5；
According to the method test in embodiment 2, after tested, reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm)
Afterwards, after TCE removal rate reaches 56%, reaction 64 days in the anaerobism underground water containing TCE, TCE in the anaerobism underground water containing TCE
Removal rate reaches 99%.
Embodiment 8
Present embodiments provide a kind of method for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, such as Fig. 1
It is shown, include the following steps:
S1, bentonite is mixed with water, the mass ratio of bentonite and water is 1.5:50, and mud is made；
The pollution source area S2, DNAPL buried depth is 10~30m, by the way of high-pressure injection, by the slurry prime in step S1
Into the pollution source area DNAPL downstream water-bearing layer, vertical divider wall is formed, the infiltration coefficient of vertical divider wall is 1 × 10-7Cm/s,
Thickness 16cm, to water barrier, trichloro ethylene is fixed in the diffusion mobility of blocking dna PL pollution sources for the bottom of vertical divider wall；
S3, the medicament in embodiment 1 is injected into the pollution source area DNAPL, controls persulfate and DNAPL pollution sources in medicament
The mass ratio of trichloro ethylene is 300:5, trichloro ethylene therein of degrading in area；
After tested, after reacting 64 days, TCE removal rate reaches 98% or more in the pollution source area DNAPL.
Embodiment 9
A kind of method for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water is present embodiments provided, including
Following steps:
S1, bentonite is mixed with water, the mass ratio of bentonite and water is 1:60, and mud is made；
The pollution source area S2, DNAPL buried depth is 10~30m, by the way of high-pressure injection, by the slurry prime in step S1
Into the pollution source area DNAPL downstream water-bearing layer, vertical divider wall is formed, the infiltration coefficient of vertical divider wall is 1 × 10-8Cm/s,
Thickness 19cm, to water barrier, trichloro ethylene is fixed in the diffusion mobility of blocking dna PL pollution sources for the bottom of vertical divider wall；
S3, the medicament in embodiment 2 is injected into the pollution source area DNAPL, controls persulfate and DNAPL pollution sources in medicament
The mass ratio of trichloro ethylene is 500:1, trichloro ethylene therein of degrading in area；
After tested, after reacting 64 days, TCE removal rate reaches 98% or more in the pollution source area DNAPL.
Embodiment 10
A kind of method for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water is present embodiments provided, including
Following steps:
S1, bentonite is mixed with water, the mass ratio of bentonite and water is 2:40, and mud is made；
The pollution source area S2, DNAPL buried depth is 10~30m, by the way of high-pressure injection, by the slurry prime in step S1
Into the pollution source area DNAPL downstream water-bearing layer, vertical divider wall is formed, the infiltration coefficient of vertical divider wall is 1 × 10-9Cm/s,
Thickness 9cm, to water barrier, trichloro ethylene is fixed in the diffusion mobility of blocking dna PL pollution sources for the bottom of vertical divider wall；
S3, the medicament in embodiment 3 is injected into the pollution source area DNAPL, controls persulfate and DNAPL pollution sources in medicament
The mass ratio of trichloro ethylene is 500:1, trichloro ethylene therein of degrading in area；
After tested, after reacting 64 days, TCE removal rate reaches 98% or more in the pollution source area DNAPL.
Embodiment 11
Present embodiments provide a kind of method for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, such as Fig. 2
It is shown, include the following steps:
S1, bentonite is mixed with water, the mass ratio of bentonite and water is 1.5:55, and mud is made；
The pollution source area S2, DNAPL buried depth < 10m, by the way of cofferdam, by the slurry prime in step S1 to DNAPL dirt
It contaminates in the aeration zone around source region, in aeration zone and forms vertical divider wall around the pollution source area DNAPL and level obstructs
Wall, the infiltration coefficient of vertical divider wall are 1 × 10-7Cm/s, thickness 16cm, the infiltration coefficient of horizontal barrier wall are 1 × 10-7cm/
S, thickness 16cm, the diffusion mobility of blocking dna PL pollution sources, fixed trichloro ethylene；
S3, the medicament in embodiment 4 is injected into the pollution source area DNAPL, controls persulfate and DNAPL pollution sources in medicament
The mass ratio of trichloro ethylene is 400:3, trichloro ethylene therein of degrading in area；
After tested, after reacting 64 days, TCE removal rate reaches 98% or more in the pollution source area DNAPL.
Embodiment 12
A kind of method for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water is present embodiments provided, including
Following steps:
S1, bentonite is mixed with water, the mass ratio of bentonite and water is 2:50, and mud is made；
The pollution source area S2, DNAPL buried depth < 10m, by the way of cofferdam, by the slurry prime in step S1 to DNAPL dirt
It contaminates in the aeration zone around source region, in aeration zone and forms vertical divider wall around the pollution source area DNAPL and level obstructs
Wall, the infiltration coefficient of vertical divider wall are 1 × 10-8Cm/s, thickness 14cm, the infiltration coefficient of horizontal barrier wall are 1 × 10-8cm/
S, thickness 14cm, the diffusion mobility of blocking dna PL pollution sources, fixed trichloro ethylene；
S3, the medicament in embodiment 5 is injected into the pollution source area DNAPL, controls persulfate and DNAPL pollution sources in medicament
The mass ratio of trichloro ethylene is 450:2, trichloro ethylene therein of degrading in area；
After tested, after reacting 64 days, TCE removal rate reaches 98% or more in the pollution source area DNAPL.
Comparative example 1
This comparative example provides a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, with real
Example 1 is applied, only difference is that: bentonite is calcium-base bentonite in this comparative example, limited purchased from the permanent safe bentonite in Zhangjiakou
Responsible company；
Simulation application environment has by the medicament in this comparative example applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter calcium-base bentonite, guarantees the mass ratio of TCE in calcium-base bentonite, persulfate and the anaerobism underground water containing TCE in medicament
For 4000:384:2, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE in the anaerobism underground water containing TCE
After removal rate reaches 31%, reaction 64 days, TCE removal rate reaches 72% in the anaerobism underground water containing TCE.
Comparative example 2
This comparative example provides a kind of medicament for synchronizing trichloro ethylene in fixed and reduction soil and/or underground water, with real
Example 1 is applied, only difference is that: bentonite is sodium bentonite, Na in sodium bentonite in this comparative example+Content is
5wt%, total content of organic carbon 9mg/L, pH 10.6, partial size are 150 μm；
Simulation application environment has by the medicament in this comparative example applied in the anaerobism underground water containing TCE of 10mg/L
Body application method is as follows: by medicament persulfate and water add into the anaerobism underground water containing TCE of 10mg/L, then plus
Enter bentonite, guarantee that the mass ratio of TCE in bentonite, persulfate and the anaerobism underground water containing TCE in medicament is 4000:
384:2, after being reacted 8 days under the conditions of room temperature, normal pressure, oscillation (250rpm), TCE removal rate in the anaerobism underground water containing TCE
After reaching 40%, reaction 64 days, TCE removal rate reaches 81% in the anaerobism underground water containing TCE.
Test example 1: bentonite couples the application that persulfate cuts down underground water pollution source region trichloro ethylene
1, experimental material and instrument: TCE: Beijing Chemical Plant (purity >=99.5%)；Sodium peroxydisulfate: Beijing Chemical Plant (point
It analyses pure)；Potassium iodide: Beijing Chemical Plant (analysis is pure)；Sodium bicarbonate: Beijing Chemical Plant (analysis is pure)；Sodium chloride: Beijing Chemical Plant
(analysis is pure)；Potassium sulfate: Beijing Chemical Plant (analysis is pure)；Magnesium sulfate: Beijing Chemical Plant (analysis is pure)；Calcium sulfate: Beijing chemical industry
Factory (analysis is pure)；Methanol: DIKMA company (purity >=99.9%), Honeywell Corp. USA's (chromatographically pure)；Alternate standard is mixed
Close object: Chem Service company, the U.S. (2000 μ g/mL are in methanol)；The mixed mark of 54 component volatilization organic matters: U.S. Chem
Service company (2000 μ g/mL are in methanol)；Bentonite: Chinese medicines group chemical reagent limited liability company (sodium base)；Experiment is used
Water: ultrapure water；Helium: Beijing Hua Yuan gas Co., Ltd (purity 99.999%)；Gas chromatograph-mass spectrometer: Agilent,
6890/5973N, the U.S.；Headspace autosampler: Agilent, G1888, the U.S.；Constant-temperature shaking incubator: Fu Ma, QYC-
2102C, China；Table-type low-speed centrifuge: Hunan instrument, L550, China；Table model high speed centrifuge: capital is vertical, LG16-W (I), China；
Ultraviolet specrophotometer: Shimadzu, UV-1800, Japan；Anaerobic box glove box: COY, 14500Coy Drive, the U.S.；pH
Meter: Sartorius, PB-10, Germany；Oxidation-reduction potentiometer: Clean, ORP30, the U.S.；Micro-sampling pin: Hamilton,
10,25,100,1000 μ L, Switzerland；
2, it tests:
(1) bentonite and persulfate cut down the performance under short-term load of trichloro ethylene in underground water:
Divide and 0.4g bentonite is taken to be placed in a series of 20mL tool lid (inner liner polytetrafluoroethylene/silica gel dottle pin) screw thread mouth brown glass
In glass bottle；20mL is added and drives oxygen ultrapure water；100 μ L 476g/L sodium peroxydisulfate mother liquors are added, guarantee that persulfate initial concentration is
1.9g/L；5 μ L 40.0g/L TCE mother liquors are added, guarantee TCE initial concentration is 10mg/L；Vial is placed in constant temperature oscillator
(250rpm, 25 ± 1.0 DEG C) periodically takes out in 8 days and is centrifuged (3000rpm, 20min)；Supernatant is taken to detect TCE, 1,1- bis-
Vinyl chloride, 1,2- dichloroethylene, vinyl chloride and pH；Every group of experiment sets 3 in parallel；
The short-term removal effect of TCE caused by medicament in embodiment 1 is shown in that Fig. 3, the fitting of related kinetic linearity are shown in Fig. 4, single
The short-term removal effect of TCE caused by one bentonite is shown in Fig. 3, and the variation of TCE dechlorination product caused by the medicament in embodiment 1 is shown in Table 1,
Fig. 5 is shown in the variation of pH caused by medicament in embodiment 1.When reacting 5 days, single bentonite is only 3% to TCE removal rate, is shown
Bentonitic suction-operated is faint (Fig. 3).Under normal temperature and pressure, single sodium peroxydisulfate is also only capable of removing a small amount of TCE.Reaction 8 days
When, bentonite and persulfate are combined to TCE removal rate up to 56%, illustrate that persulfate being capable of the efficient oxidation degradation TCE (figure
3).Bentonite and persulfate combination oxidative degradation TCE meet pseudo-first order reaction kinetics, and degradation rate constant is 0.094
(d-1) (Fig. 4).On the other hand, when bentonite and persulfate are combined, be not detected vinylidene chloride, 1,2-dichloroethene,
3 kinds of dechlorination products (table 1) such as vinyl chloride, it was demonstrated that TCE is by permineralization.In another aspect, in bentonite and persulfate reactant
In system, under conditions of initial pH is 10.5, pH still maintains 10.2 (Fig. 5) after 8 days.As it can be seen that system pH is with the reaction time
Variation it is little, illustrate bentonite can guarantee system be in stable alkaline environment, and then be advantageously implemented alkali activation over cure
Hydrochlorate.
Caused TCE dechlorination product variation in 1 embodiment 1 of table
Note: ND expression is not detected.
(2) bentonite and persulfate cut down the long-term behaviour of trichloro ethylene in underground water:
Divide and 0.4g bentonite is taken to be placed in a series of 20mL tool lid (inner liner polytetrafluoroethylene/silica gel dottle pin) screw thread mouth brown glass
In glass bottle；20mL is added and drives oxygen ultrapure water；100 μ L 476g/L sodium peroxydisulfate mother liquors are added, guarantee that persulfate initial concentration is
1.9g/L；5 μ L 40.0g/L TCE mother liquors are added, guarantee TCE initial concentration is 10mg/L；Vial is placed in constant temperature oscillator
(250rpm, 25 ± 1.0 DEG C) periodically takes out in 64 days and is centrifuged (3000rpm, 20min)；Supernatant is taken to detect TCE, S2O8 2-、
PH and Eh；Every group of experiment sets 3 in parallel.
The long-term removal effect of TCE caused by medicament in embodiment 1, reaction system Eh variation, reaction system pH variation and
Fig. 6, Fig. 7, Fig. 8 and Fig. 9 are shown in the variation of persulfate residual quantity respectively.As the reaction time extends to 64 days, the medicine in embodiment 1
Agent is to TCE removal rate up to 100% (Fig. 6).System pH is gradually decreased, but luffing is little, is down to 9.3 (64 days by initial 10.5
When) (Fig. 7).Although persulfate can be with generation H in oxidative degradation TCE+(formula 1), but bentonite is shown very by force
Buffer function, cause system pH variation little.First 15 days, system Eh gradually rose, and was increased to by initial 60.1mV
225.6mV；After 15 days, it is high when Eh, when low, numerical value between 174.0~225.7mV (Fig. 8).The raising of Eh is further proved
Bentonite can be promoted persulfate to be activated and be generated SO with the alkalinity of maintenance system, oxidation environment4 ·-, and then cause SO4 ·-Turn
Turn to OH.TCE is completely removed (Fig. 6) after 64 days, however still remains a large amount of persulfate in system (residual rate is big
In 90%) (Fig. 9).Articulated system pH, Eh and persulfate residual quantity, thus it is speculated that the system still has the energy of oxidative degradation TCE
Power.
SO4 ·-+C2HCl3+4H2O→2CO2+9H++3Cl-+6SO4 2- (1)
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
- Synchronize medicament that is fixed and cutting down trichloro ethylene in soil and/or underground water 1. a kind of, including bentonite, persulfate and The mass ratio of water, the bentonite and persulfate is 3000~5000:300~500, and the mass ratio of the bentonite and water is 1~2:40~60；The bentonite is sodium bentonite, Na in the sodium bentonite+Content is 2wt%~4wt%, total content of organic carbon It is 10.0~11.0 for 10~15mg/L, pH, partial size is 75~180 μm.
- 2. medicament according to claim 1, which is characterized in that the mass ratio of the bentonite and persulfate be 3800~ The mass ratio of 4200:350~400, the bentonite and water is 1~2:45~55；The bentonite is sodium bentonite, Na in the sodium bentonite+Content is 2.5wt%~3wt%, and total organic carbon contains Amount is 13~14mg/L, and pH is 10.5~10.8, and partial size is 120~150 μm.
- 3. medicament according to claim 1 or 2, which is characterized in that the persulfate is potassium peroxydisulfate and/or persulfuric acid Sodium, purity >=98wt% of the persulfate.
- 4. medicament according to claim 3, which is characterized in that the persulfate is potassium peroxydisulfate and sodium peroxydisulfate, institute The mass ratio for stating potassium peroxydisulfate and sodium peroxydisulfate is 1:(4-5).
- 5. a kind of synchronize fixed and cut down three in soil and/or underground water using medicament of any of claims 1-4 The method of vinyl chloride, includes the following steps:S1, bentonite is mixed with water, mud is made；S2, using cofferdam or high-pressure injection mode, by the slurry prime in step S1 to the pollution source area DNAPL surrounding soil and ground In lower aqueous medium, forms vertical divider wall and/or three chloroethenes are fixed in horizontal barrier wall, the diffusion mobility of blocking dna PL pollution sources Alkene；S3, the medicament is injected into the pollution source area DNAPL, trichloro ethylene therein of degrading.
- 6. according to the method described in claim 5, it is characterized in that, the mass ratio of bentonite and water is 1~2:40 in step S1 ~60.
- 7. method according to claim 5 or 6, which is characterized in that in step S2, the infiltration coefficient of the vertical divider wall ≤1×10-7Cm/s, 9~19cm of thickness；Infiltration coefficient≤1 × 10 of the horizontal barrier wall-7Cm/s, 9~19cm of thickness.
- 8. the method according to any one of claim 5-7, which is characterized in that in step S3, persulfuric acid in the medicament The mass ratio of trichloro ethylene is 300~500:1~5 in salt and the pollution source area DNAPL.
- 9. the method according to any one of claim 5-8, which is characterized in that in step S2, when the DNAPL pollution sources Area's buried depth < 10m, is implemented by the way of cofferdam；Or,In step S2, when the pollution source area DNAPL buried depth is 10~30m, by the way of high-pressure injection.
- 10. the method according to any one of claim 5-9, which is characterized in that arrive the slurry prime in step S1 In aeration zone around the pollution source area DNAPL, in aeration zone and formation vertical divider wall and water around the pollution source area DNAPL Flat barrier wall；Or,By the slurry prime in step S1 into the pollution source area DNAPL downstream water-bearing layer, vertical divider wall is formed.
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