CN105923963B - The activity covering restorative procedure in situ of persistence organic pollutant in a kind of deposit - Google Patents
The activity covering restorative procedure in situ of persistence organic pollutant in a kind of deposit Download PDFInfo
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- CN105923963B CN105923963B CN201610425389.3A CN201610425389A CN105923963B CN 105923963 B CN105923963 B CN 105923963B CN 201610425389 A CN201610425389 A CN 201610425389A CN 105923963 B CN105923963 B CN 105923963B
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- magnetic
- active carbon
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- organic pollutant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
Abstract
The invention discloses a kind of activity covering restorative procedures in situ of persistence organic pollutant in deposit; this method is using magnetic-particle active carbon as covering material; magnetic-particle active carbon not only can persistence organic pollutant (POPs) effectively in immobilized sediment, but also have the characteristics that converted in-situ and the POPs that degrades.Its covering method is to realize that magnetic-particle active carbon interlaminates coverage mode by using the demagnetization control of filling of underwater electric permanent-magnet suction disc, convenient for the installation and replacement of covering material；Influence of the water volume flow rate to covering is reduced using moveable enclosure frame；The orientation of marine sediments, positioning, uniform fold are realized using underwater electric permanent-magnet suction disc release and Underwater Imaging instrument combination mode, effectively reduce overwrite procedure in situ to the adverse effect of overlying water.
Description
Technical field
The invention belongs to contaminated sediment remediation recovery technique fields, and in particular to it is a kind of using can the activity of Magnetic Isolation cover
Cover material home position strengthening repairs the technology of persistence organic pollutant in deposit, especially suitable for by persistence organic pollutant
The reparation in seriously polluted river, estuary of the lake and lake sediment.
Background technique
Persistence organic pollutant (POPs) is difficult to degrade, can transmit at a distance, bioaccumulation, carcinogenic cause because it has
The characteristics such as mutability and endocrine disruption, lake, river pollution problem caused by these compounds have caused various countries scientific
The highest attention on boundary, government and street levels.Therefore POPs pollution effectively in control and reparation deposit, improves water body environment quality
Be particularly important with it is urgent.At present to the control and reparation of POPs in water body deposit, mainly use dredging, cover in situ with
And the mode of controlled spontaneous recovery technology.Though dredging is quick, easily causes marine sediments and rise and to pollution deposit
The secondary pollutions problems such as the subsequent strange land disposition of object.Compared with dredging technology and controlled spontaneous recovery technology, soverlay technique tool in situ
There are lesser ecological risk and good repairing effect.Currently, the covering material used mainly has natural material, it is such as clean heavy
Product object, soil, sand, gravel etc., wherein sand is the most commonly used material.It can also be using natural zeolite and river sand (as specially
Disclosed in sharp document CN102531197B " bioactive multilayer covering remediation method for contaminated sediment "), ferrihydrite, calcite,
Geotextiles and local river sand (" the active covering side for deposit in-situ immobilization as disclosed in patent document CN103613257A
Method ") and iron tailings particle and cement (" the rivers and lakes heavy metal polluted bed mud as disclosed in patent document CN102775035B
In-situ covering method and device ") etc..Although these covering materials can effective fixed-contamination object, do not have contaminant degradation
Ability, and material organic carbon content itself is low, limited sorption capacity.And more active covering material is used at present, such as activity
Charcoal, can be with efficient absorption and fixed-contamination object, but there are effects after POPs adsorption saturation to be substantially reduced, in practical application there is also
Difficult problem is separated, and the long-term existence of active carbon has a negative impact to aquatic ecosystem.For can Magnetic Isolation magnetic
Property active carbon use, be focused only on Adsorption Organic Pollutants in Wastewater at present, heavy metal and gold extract.In addition,
The coverage mode of soverlay technique in situ mainly has: mobile barge surface layer dispenses mode, water-jet Surface mulch mode and machine
Topple over mode etc. in tool equipment surface layer.These coverage modes, which only directly incline covering material, is sprinkling upon the surface of contaminated sediment remediation, by
The influence of water flow is difficult to realize to be completely covered and orients, positions covering.And directly incline spread covering material be easy to cause it is contaminated
Sediment resuspension adversely affects water quality.
Summary of the invention
For the prior art is defective or insufficient, the purpose of the present invention is to provide persistence in a kind of deposit to have
The activity covering restorative procedure in situ of machine pollutant, this method can be realized the efficient of persistence organic pollutant in deposit and catch
It obtains, converted in-situ and degradation and the characteristics of Magnetic Isolation, and covering material is easily installed and replaced, realizes marine sediments
Orientation, uniform fold and interlaminates coverage mode at positioning.
The present invention is using active covering material in situ, to contaminated sediment remediation using coverage mode is interlaminated, by adopting
Orientation, the positioning uniform fold of marine sediments are realized with underwater electric permanent-magnet suction disc release and Underwater Imaging instrument combination mode
It repairs, is realized especially by following technical scheme:
(1) select magnetic-particle active carbon as the covering material of marine sediments.
The granular activated carbon is coal quality column-shaped active carbon, 1.5 mm of partial size.
The magnetic-particle active carbon is combined by coal quality column-shaped active carbon and ferroferric oxide magnetic fluid: will
FeSO4•7H2O and FeCl3•6H2O presses (Fe2+: Fe3+) molar ratio be 1:2 ratio be dissolved in deionized water, coal quality column is added
Active carbon is allowed to be sufficiently mixed.Magnetic agitation is slowly added dropwise sodium hydroxide solution under the conditions of 70 DEG C, makes solution ph
10-11 magnetic agitation 1-2 hours, then magnetic agitation reaction 8 hours, removes supernatant, obtains black precipitate, use deionization
Water and dehydrated alcohol clean repeatedly.After ethyl alcohol volatilization, dry black precipitate 24 hours under the conditions of 60 DEG C, then magnetic force is used
Stick collects magnetic-particle active carbon, and the magnetic-particle active carbon being collected into is dried 16 hours under the conditions of 80 DEG C.
(2) contaminated sediment remediation is used and interlaminates coverage mode.The cladding thickness of magnetic-particle active carbon is covering
In deposit surface layer 2-5 mm.It is obvious to POPs stress efficacy in deposit to magnetic-particle active carbon after first thin layer covering
When reduction, magnetic-particle active carbon is taken out from marine sediments using Magnetic Isolation, covers new magnetic-particle activity again
Charcoal.
(3) determining for marine sediments is realized using underwater electric permanent-magnet suction disc release and Underwater Imaging instrument combination mode
To, positioning all standing.
The underwater use electric permanent-magnet suction disc release, is controlled using magnetizing and demagnetizing controller, is only filling demagnetized state conversion
When be passed through instantaneous power, the course of work no longer electricity consumption, the middle work magnetic force that works after magnetizing is not by the power failures shadow such as system cut-off
It rings, table top remanent magnetism is clean, it can be achieved that quick stress release magnetic-particle active carbon after demagnetization.
The Underwater Imaging instrument is high-definition intelligent rotation underwater camera, is mounted on above mobile framework, so as to right
Coverage condition is detected.The mobile framework is the enclosure baffle that can move up and down, and reduces water volume flow rate to covering
It influences.
Good effect by adopting the above technical scheme: magnetic-particle active carbon not only has preferable absorption and separation effect
Fruit, and there is the chemical oxidation for enhancing POPs in magnetisable material, increase the biological effectiveness of POPs in deposit, be conducive to
Subsequent microbial degradation.The pili that magnetic iron ore can replace ground bacillus realizes the function of extracellular microbial exoelectron transmitting at a distance,
It further strengthens function the ability of gene cell pigment c electron transmission.Moreover, active carbon can also be used as electron acceptor or electricity
Sub- shuttle body mediates electron transfer process between microorganism and magnetic iron ore, under anaerobic bioconversion POPs.It can be seen that
Into marine sediments cover magnetic-particle active carbon be equivalent to one is increased in deposit can be with the electronics of Magnetic Isolation
Receptor, to form microbial metabolism new way inside deposit.When covering material is to POPs stress efficacy in deposit
When reduction, has the covering material of Magnetic Isolation convenient for covering and replacing again.Covering material using electromagnetic releasing and under water at
Orientation, positioning all standing as combination realization marine sediments, reduce marine sediments settling flux and make to water quality
At detrimental effect.
Detailed description of the invention
The magnetic-particle active carbon of Fig. 1 preparation.
The content of Fig. 2 polycyclic aromatic hydrocarbons in sediments (PAHs) with the cover time variation.
The structural representation of the activity covering restorative procedure in situ of persistence organic pollutant in deposit Fig. 3 of the invention
Figure；Wherein: 1, using electric permanent-magnet suction disc, 2, magnetizing and demagnetizing controller, 3, magnetic-particle active carbon, 4, frame, 5, Underwater Imaging under water
Instrument.
Specific embodiment
Technical solution of the present invention is further described below in conjunction with specific drawings and examples.
Embodiment 1
The preparation of magnetic-particle active carbon: 3.140 g FeSO are weighed respectively4•7H2O and 6.105 g FeCl3•6H2O is molten
Solution is added 4.5 g coal quality column-shaped active carbons, is allowed to be sufficiently mixed in 100 mL deionized waters.Magnetic agitation under the conditions of 70 DEG C
5 mol/L sodium hydroxide solutions are slowly added dropwise, make solution ph 10-11, magnetic agitation 1-2 hours, then magnetic agitation
Reaction 8 hours removes supernatant, obtains black precipitate, cleaned repeatedly with deionized water and dehydrated alcohol.It volatilizees to ethyl alcohol
Afterwards, dry black precipitate 24 hours under the conditions of 60 DEG C, then magnetic-particle active carbon, the magnetic being collected into are collected using magnetic bar
Property granular activated carbon is dried 16 hours under the conditions of 80 DEG C.The magnetic-particle active carbon of preparation is as shown in Figure 1.The particle of measurement is living
Property charcoal and magnetic-particle active carbon specific surface area and average hole hold it is as shown in table 1.The specific surface area of granular activated carbon and aperture
Respectively 487.361 m2/g,2.619 nm；Increase in contrast, the specific surface area of magnetic-particle active carbon reduces, aperture is opposite
Greatly.Show that most of micropore of active carbon is occupied by magnetic component, the filling of magnetic component increases aperture, is successfully prepared magnetic
Property mesoporous particles active carbon, and prepare composite material have preferable magnetic property (such as Fig. 1).
The pore property of table 1. granular activated carbon and magnetic-particle active carbon
Embodiment 2
Acquire the S & W sample in the high region (such as East Taihu Lake flood port) of lake river mouth area POPs content.Research is magnetic
Conversion efficiency of the addition of granular activated carbon to polycyclic aromatic hydrocarbons in sediments (PAHs).Using 150 mL glass culture roller bottles, often
80 g wet deposition objects and 50 mL overlying waters are added in a reaction flask, sets different disposal group: being not added with magnetic-particle active carbon
Deposit as a control group；Other processing groups add 3.6% magnetic-particle active carbon (based on deposit dry weight).Glass is trained
Feeding roller bottle is placed in roller bottle incubator (about 3 rpm of rolling speed) culture.Using destructive sample mode, sampling time difference
For 0 d, 25 d, 68 d, 95 d, 115 d.Measure remaining PAHs content (such as Fig. 2) in deposit.It tests, sinks by 95 d
The removal rate of PAHs is up to 90% or more in product object.PAHs stress efficacy in deposit is presented in magnetic-particle active carbon when 115 d
The phenomenon that reduction.Therefore, using coverage mode is interlaminated after marine sediments cover about 3 months in situ, Magnetic Isolation is former
Some magnetic-particle active carbons cover new magnetic-particle active carbon again.
Embodiment 3
Fig. 3 gives the structure of the activity covering restorative procedure in situ of persistence organic pollutant in deposit of the invention
Schematic diagram.Electric permanent-magnet suction disc 1 is used to be in magnetization status under water when covering in situ, magnetic-particle active carbon 3 is firmly adsorbed on electricity
The bottom of permanent magnetic chuck 1.In covering point position, mobile framework 4 is discharged downwards, and carrying out enclosing to covering point can be effectively reduced water
Influence of the body flow velocity to covering, while the image frame implementing demagnetization control 2 fed back according to Underwater Imaging instrument 5, it is ensured that magnetic
Grain active carbon uniformly, is smoothly covered on the surface layer of marine sediments.
Claims (7)
1. the activity covering restorative procedure in situ of persistence organic pollutant in a kind of deposit, it is characterised in that: the method
It is inhaled to contaminated sediment remediation using coverage mode is interlaminated by using underwater electric permanent magnetism using active covering material in situ
Disk release and Underwater Imaging instrument combination mode realize the orientation of marine sediments, positioning uniform fold reparation；The original
The active covering material in position is magnetic-particle active carbon；
The magnetic-particle active carbon is combined by coal quality column-shaped active carbon and ferroferric oxide magnetic fluid；
The specific complex method of magnetic-particle active carbon is as follows: by FeSO4•7H2O and FeCl3•6H2O presses (Fe2+: Fe3+) rub
You are added coal quality column-shaped active carbon, are allowed to be sufficiently mixed than being that the ratio of 1:2 is dissolved in deionized water；Magnetic under the conditions of 70 DEG C
Power stirring is slowly added dropwise sodium hydroxide solution, makes solution ph 10-11, and magnetic agitation 1-2 hours, then magnetic agitation is anti-
It answers 8 hours, removes supernatant, obtain black precipitate, cleaned repeatedly with deionized water and dehydrated alcohol；After ethyl alcohol volatilization,
Dry black precipitate 24 hours under the conditions of 60 DEG C, then magnetic-particle active carbon, the magnetism being collected into are collected using magnetic bar
Granular activated carbon is dried 16 hours under the conditions of 80 DEG C.
2. the activity covering restorative procedure in situ of persistence organic pollutant in a kind of deposit according to claim 1,
It is characterized by: after first thin layer covering, to magnetic-particle active carbon to persistence organic pollutant stress efficacy in deposit
When being substantially reduced, magnetic-particle active carbon is taken out from marine sediments using Magnetic Isolation, covers new magnetic-particle again
Active carbon.
3. the activity covering in situ reparation side of persistence organic pollutant in a kind of deposit according to claim 1
Method, it is characterised in that: the partial size of the coal quality column-shaped active carbon is 1.5 mm.
4. the activity covering in situ reparation side of persistence organic pollutant in a kind of deposit according to claim 1
Method, it is characterised in that: the cladding thickness of magnetic-particle active carbon is to be covered in deposit surface layer 2-5 mm.
5. the activity covering in situ reparation side of persistence organic pollutant in a kind of deposit according to claim 1
Method, it is characterised in that: the underwater use electric permanent-magnet suction disc release is controlled using magnetizing and demagnetizing controller, only filling demagnetization shape
State is passed through instantaneous power, the course of work no longer electricity consumption when converting.
6. the activity covering restorative procedure in situ of persistence organic pollutant in a kind of deposit according to claim 1,
It is characterized by: the Underwater Imaging instrument is high-definition intelligent rotation underwater camera, it is mounted on above mobile framework.
7. the activity covering restorative procedure in situ of persistence organic pollutant in a kind of deposit according to claim 6,
It is characterized by: the mobile framework is the enclosure baffle moved up and down.
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| WO2002078871A1 (en) * | 2001-03-28 | 2002-10-10 | Lion Corporation | Method of purifying contaminated soil |
| CN1234451C (en) * | 2002-11-13 | 2006-01-04 | 中国科学院生态环境研究中心 | Preparing Method for magnetic active carbon used for water treatment |
| CN100386141C (en) * | 2005-07-20 | 2008-05-07 | 上海自来水市北科技有限公司 | Composite absorption material for removing arsenic from water and its prepn. method |
| CN101289255A (en) * | 2007-04-18 | 2008-10-22 | 南开大学 | Reactive barrier technology for high-efficiency repairing organic pollution deposit in water |
| JP5276429B2 (en) * | 2008-12-25 | 2013-08-28 | エコム株式会社 | Contaminated soil area improvement method |
| CN101786713B (en) * | 2010-03-05 | 2012-01-11 | 泉州师范学院 | Emergency restoring process for pollution of water body, substrate sludge and tidal flat by heavy metal |
| CN101972629B (en) * | 2010-11-01 | 2012-03-21 | 重庆大学 | Preparation method of coal-based magnetic activated carbon and coal-based magnetic activated carbon |
| CN103611496B (en) * | 2013-11-12 | 2016-08-17 | 南京工业大学 | A kind of magnetic carbon-supported catalyst and application |
| DE102014100850B4 (en) * | 2014-01-24 | 2015-09-03 | Leibniz-Institut für Agrartechnik Potsdam-Bornim e.V.(ATB) | Magnetisable particles, process for their preparation and their use |
| CN104528868A (en) * | 2014-12-31 | 2015-04-22 | 华南师范大学 | Application of magnetic particles in in-situ treatment of eutrophic water and sedimentary phosphate |
| CN105536703A (en) * | 2015-12-25 | 2016-05-04 | 华中农业大学 | Preparation method for magnetic biological carbon by one-step synthesis |
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