CN105621824B - A method of it is in situ to administer river bottom mud heavy metal - Google Patents
A method of it is in situ to administer river bottom mud heavy metal Download PDFInfo
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- CN105621824B CN105621824B CN201510973884.3A CN201510973884A CN105621824B CN 105621824 B CN105621824 B CN 105621824B CN 201510973884 A CN201510973884 A CN 201510973884A CN 105621824 B CN105621824 B CN 105621824B
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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
- C02F11/004—Sludge detoxification
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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- Water Supply & Treatment (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
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Abstract
The invention discloses a kind of methods in situ for administering river bottom mud heavy metal, this method is that cuboid brick, column or graininess is made in nano-porous ceramic composite material, it is implanted by certain arrangement or is fixed in river bottom mud, adsorption treatment is carried out to heavy metal ion in river bottom mud；Heavy metal pollution in river bottom mud, and recyclable heavy metal ion can be effectively removed, without destroying the original ecosystem in river, the water intaking water safety of the stabilization in riverbed, the safety of two sides river levee and lower reaches of river is not influenced, this method safety, low cost, it is easy to operate, it is suitable for promoting the use of.
Description
Technical field
The present invention relates to a kind of methods in situ for administering river bottom mud heavy metal, belong to river Heavy Metal Pollution technology
Field.
Background technique
River bottom mud refers to the superficial deposit substance of water bottom, is made of silt, soil, humus and microorganism etc.,
It is main life area and the food source of river mesobenthos, is the important component part of river channel ecology system.River bottom
Mud is component part important in river ecosystem, has vital effect to river water purification of water quality, with society
It largely can be discharged into river with economic rapid development, sanitary sewage, industrial wastewater etc., mercury is got worse, long
The accumulation of phase makes pollutant component complexity in bed mud, it is difficult to remove.Especially industrial development bring heavy metal pollution, because of a huge sum of money
Category will not be biodegradable, and when environmental change, the Heavy Metals being deposited in bed mud will occur to convert and be discharged into water body
In cause secondary pollution.Heavy metal has bioaccumulation simultaneously, and heavy metal, which passes through biological metabolism, can retain, accumulates and move
The harm for generating intoxicating teratogenesis in organism is moved, not only endangers the benthon in river, while seriously threatening the body of people
Body health.
Currently mainly there are peripheral doses, chemical remediation and biological prosthetic to the recovery technique of Mixing Coefficient in Rectangular Channels both at home and abroad.Object
Reason restorative procedure can be divided into situ administer and administer two kinds of technologies with dystopy.Treatment process in situ include back-up sand masking, solidification masking,
Physics elution etc..Dystopy processing then includes engineering dredging, solidification landfill etc..Chemical repair method is then to utilize chemical agent and dirt
Pollutant such as is aoxidized, is restored, being precipitated at the reaction in mud, separates heavy metal from bed mud.Mainly there is redox, change
Learn the technologies such as extraction, chemical leaching.Biological restoration is using life processes such as the metabolism of animals and plants and microorganism the bottom of by
Metal uptake, precipitating in mud, change heavy metal existing forms to reduce heavy metal toxicity.
The method for administering river bottom mud at present is mainly dystopy processing, this method needs to consume a large amount of chemical agents, transport at
This height, and periphery construction site limits, it can be by big machinery, the bed mud to scoop away carries out secondary treatment, such as deals with improperly and easily makes
At secondary pollution.Therefore for the method there are more drawback, technological innovation is imperative.Sludge handling technology is more biased towards in being provided simultaneously with
The development trend of economic benefit and social benefit.
A kind of " ephemeral stream heavy metal polluted bed mud is disclosed in the Chinese patent of publication number 201510236655.3
Dredging method ", the technology build mud reservoir, installation elevator pump etc., wash away water pump or soil using high pressure by section cofferdam enclosing
Work machinery carries out engineering dredging operation to bed mud.Dredging can permanently remove heavy metal in bed mud, but this method project amount is big, throw
Enter it is more, and carry out bed mud needs be further processed, deal with improperly and easily cause secondary pollution.
It is disclosed in 201410249133.2 Chinese patent " at a kind of immobilization of compound heavy metal polluted bed mud
Reason method ", the technology are prepared into solidification clod by the way that various medicaments are added in bed mud, then transport to other places and fill, this
Though method process cycle is short, transportation cost is high, and the chemical agent added has the potential risk of secondary pollution.
Disclosed in 201110138736.1 Chinese patent " a method of heavy metal Cd in removal river bottom mud ",
The Technology application is biological prosthetic to the progress of microorganism leaching technology, is made and is given birth to as microorganism leaching bacterium using Thiobacillus ferrooxidans
The inoculation liquid of object leaching is aerated and stirs after mixing inoculation liquid with river bottom mud to be processed, is removed heavy metal Cd.This
Method will not destroy nutrient in bed mud, but microculture condition is harsh, and is not easy macro-control.
Peripheral doses technology can bring apparent regulation effect, but project amount is big, and treatment cost is high.The drawbacks of chemical remediation
It is to consume a large amount of chemical agents, there are certain toxics, and complicated operation, and it is larger to the side effect of bed mud, it easily causes
Secondary pollution.And the condition of microculture is relatively stringenter in bioremediation technology and is not easy to manipulate, and the growth cycle of plant
Long, growth conditions has limitation.
Summary of the invention
For defect existing for the existing recovery technique to river heavy metal pollution, the purpose of the invention is to provide
It is a kind of to effectively remove and recycle heavy metal pollution in river bottom mud, and do not destroy the original ecosystem in river, do not influence river
Stabilization, the method for the water intaking water safety of the safety of two sides river levee and lower reaches of river of bed, this method safety, low cost, operation
Simplicity is suitable for promoting the use of.
In order to achieve the above technical purposes, the present invention provides a kind of method in situ for administering river bottom mud heavy metal, packets
Include a, b or c scheme:
Scheme a: by heavy metal adsorption column A by being spaced in 1~4 meter of implantation river bottom mud in length and breadth, implantation depth is that column cap is high
0.05~0.30 meter of river bottom mud surface layer out carries out adsorption treatment to heavy metal ion in river bottom mud；
The heavy metal adsorption column A is made of upper hollow cylindrical body and lower part solid cone, hollow cylinder and
Solid cone is made of nano-porous ceramic composite material；Each heavy metal adsorption column A is by 5~30 kilograms of nano-porous ceramics
Composite material is made；
Scheme b: by heavy metal adsorption column B by being spaced in 1~4 meter of implantation river bottom mud in length and breadth, implantation depth is that column cap is high
0.05~0.30 meter of river bottom mud surface layer out；
The heavy metal adsorption column B includes the column cover and lower part solid cone outside top cylinder and cylinder；
The cylinder is made of inside and outside double layer hollow prism, region between outer hollow prism body and interior hollow prism body
Filled with nano-porous ceramic composite material granular；It is intensively distributed on the post jamb of outer hollow prism body and interior hollow prism body
Aperture；
Alternatively, the cylinder is made of inside and outside double layer hollow cylindrical body, outer hollow cylinder and interior hollow cylinder it
Between area filling have nano-porous ceramic composite material granular；It is intensive on the post jamb of outer hollow cylinder and interior hollow cylinder
Aperture is distributed with；
The nano-porous ceramic composite material granular is dispensed with mesh bag, is filled in outer hollow prism body and interior hollow rib
Region or it is filled in region between outer hollow cylinder and interior hollow cylinder between cylinder, in each heavy metal adsorption column B
Loading is 2~30 kilograms；
After in heavy metal adsorption column B implantation river bottom mud, column cover is removed, heavy metal in river bottom mud is carried out at absorption
Reason；
Scheme c: (5~30) cm × (3~25) cm × (1~10) cm cuboid is made in nano-porous ceramic composite material
Brick is uniformly embedded in river bottom mud, carries out adsorption treatment to heavy metal in river bottom mud；The nanometer of every piece of cuboid brick is more
Hole ceramic composite weighs 0.2~3 kilogram, and 2~10 kilograms of nano-porous ceramics of embedment are multiple in average every cubic metre of river bottom mud
Condensation material.
The technical scheme is that a kind of method in situ for administering the heavy metal pollution in river bottom mud, this method are broken
The existing limitation of the in-situ treatment methods such as traditional back-up sand masking, solidification masking, physics elution, without to riverway cofferdam, cut
Stream etc. is under highly difficult execution conditions, i.e., implementable, and without destroying any original ecology, in selective removal river bottom mud
Heavy metal does not cause secondary pollution.Technical solution of the present invention is mainly based upon using nano-porous ceramic composite material, is utilized
Its good mechanical performance and stability, to heavy metal have preferable absorption property and it is safe and non-toxic, can be recycled
Feature.It is made into the adsorbent material with special construction, and is implanted into river bottom mud by a certain amount, it can be in river bottom mud
Heavy metal carries out adsorption treatment, and to heavy metal removal efficiency with higher.
The method in situ for administering river bottom mud heavy metal of the invention further includes following preferred embodiment:
Preferred scheme, the hollow cylinder outer diameter in scheme a are 0.10~0.30 meter, and internal diameter is 0.02~0.10 meter,
A length of 0.5~2.0 meter, a height of 0.02~0.30 meter of solid cone.
Preferred scheme is equipped with netted stainless steel cover at the top of the hollow cylinder in scheme a.
Preferred scheme, when the cylinder in scheme b is made of inside and outside double layer hollow prism, outer hollow prism body side length is
0.02~0.25 meter, the outer hollow prism body side length of interior hollow prism body side ratio is 0.01~0.15 meter short, interior hollow prism body and
Outer hollow prism body height is 0.5~2.0 meter；Column cover is hollow prism body, the outer hollow prism body side length of side ratio is long by 0.03~
It is 0.05 meter, high high consistent with interior hollow prism body and outer hollow prism body.
Preferred scheme, when the cylinder in scheme b is made of inside and outside double layer hollow cylindrical body, outer hollow circuit cylinder diameter is
0.02~0.25 meter, interior hollow cylinder diameter is 0.03~0.20 meter shorter than outer hollow circuit cylinder diameter, interior hollow circuit cylinder cylinder and
Outer hollow cylinder height is 0.5~2.0 meter；Column cover is hollow cylinder, diameter is longer by 0.03 than outer hollow cylinder diameter~
It is 0.05 meter, high high consistent with interior hollow cylinder and outer hollow cylinder.
Preferred scheme, a height of 0.02~0.30 meter of solid cone in scheme b.
Preferred scheme, the aperture of aperture described in scheme b are 1~1.5 millimeter.
Preferred scheme, the outer hollow prism body and interior hollow prism body bottom and solid cone bottom surface in scheme b are logical
Cross movable clamp groove connection: or outer hollow cylinder and interior hollow cylinder bottom and solid cone underrun movable clamp groove
Connection；Column cover bottom is connect with solid cone underrun movable clamp groove.
Preferred scheme, nano-porous ceramic composite material granular is with 0.2~2.0 kilogram of every bag of encapsulation, filling in scheme b
Region between outer hollow prism body and interior hollow prism body or be filled in outer hollow cylinder and interior hollow cylinder it
Between region.Granular materials is made in nano-porous ceramic composite material, the surface area of material can be dramatically increased, adsorption capacity obtains
To promotion.
Preferred scheme, scheme b middle column body top are equipped with inner sealing lid.For closing outer hollow prism body and interior hollow rib
Region between region or outer hollow cylinder and interior hollow cylinder between cylinder.
Preferred scheme, scheme a or scheme b or scheme c process cycle are 1~12 month.It is more preferably 4~12 months.
Content of beary metal in bed mud can be greatly reduced after period treatment.
Preferred scheme, nano-porous ceramic composite material or nano-porous ceramic composite material granular are purchase in Ge Feng
At least one of MA01, MF01, MP02 and MP01 of tech materials Co., Ltd.MA01 primary attachment cadmium, lead, zinc, mercury,
The characteristics of heavy metals such as copper, thallium, MF01 primary attachment arsenic and lead, MP01 and MP02 be in acid condition to cadmium, lead, zinc, mercury,
Copper, thallium etc. have preferable suction-operated.The nano-porous ceramic composite material that the present invention uses has hole prosperity, and (aperture is 15
Nanometer is to controllable in 200 nanometers), specific surface area height (up to 900m2/ g) the characteristics of, adsorption rate is high, adsorption capacity is big, and has
There is the physical and chemical stability of ceramics (acid and alkali-resistance, high temperature resistant, intensity are big)；Orderly have simultaneously with high density grafting in ceramic surface
Functional organic group (different organic groups there is orientation complexing and selection to adsorb different type heavy metal ion) it is organic
Molecule forms monolayer, makes it have the ability of fabulous selective absorption target heavy metal ion.Preferred nanoporous
Ceramic composite selectivity height, large amount of adsorption, maximum heavy metal adsorption capacity possess good machinery up to 400g/kg
The advantages such as intensity, safe and non-toxic harmless, without secondary pollution to environment, renewable recycling.The nanoporous that the present invention uses
For ceramic composite using nano-porous ceramic as carrier, nano aperture inner surface has intensively modified the unimolecule containing active function groups
Layer；Its working principle is that absorption, complexing, chela using the functional molecular being attached in ceramic monolith nanoscale hole hole to pollutant
The effects of conjunction, which is adsorbed, to be trapped in inside heavy-metal adsorption material, and heavy metal ion is fixed.
Preferred scheme can be taken off nanometer after heavy metal adsorption column A handles a period to heavy metal adsorption in river bottom mud
Porous ceramic composite recycles heavy metal.
Preferred scheme can be taken off nanometer after heavy metal adsorption column B handles a period to heavy metal adsorption in river bottom mud
Porous ceramic composite recycles heavy metal.
Preferred scheme, cuboid bricked nano-porous ceramic composite material is to heavy metal adsorption processing one in river bottom mud
After period, nano-porous ceramic composite material can be taken off, recycle heavy metal or without any processing, heavy metal is fixed on
Inside river bottom mud.
Preferred scheme, the method for recycling heavy metal are to pass through the nano-porous ceramic composite material for having adsorbed heavy metal
Hydrochloric acid or EDTA solution are eluted, and heavy metal is recycled.The process for recycling heavy metal is that will adsorb the nanometer of heavy metal ion
Porous ceramic composite hydrochloric acid or the elution of EDTA solution, obtain the solution containing heavy metal ion, regenerate nano-porous ceramic
Composite material is reused.The recycling of heavy metal is not only realized by hydrochloric acid or EDTA solution, and makes nano-porous ceramic
Composite material regeneration, recycling greatly reduce processing cost.Hydrochloric acid or EDTA solution concentration are inhaled according to heavy metal absorbent
The amount of attached heavy metal is suitably adjusted.
Heavy metal adsorption column A and the lower part heavy metal adsorption column B of the invention is designed to solid cone, is conducive to adsorption column
Implantation and fixation in bed mud.
Heavy metal adsorption column A and heavy metal adsorption column B upper design of the invention at hollow prism body or hollow cylinder,
It is internal with cavity.Its working principle is that containing in bed mud behind heavy metal adsorption column A and heavy metal adsorption column B implantation river
The water of heavy metal constantly passes through cylinder post jamb and penetrates into column body cavity, the heavy metal quilt when water passes through cylinder post jamb, in water
The absorption of nano-porous ceramic composite material, purified water enter column body cavity, and the water in column body cavity and river bottom
There are pressure differences for the flowing water in portion, and the water of cylinder cavity inside is made constantly to flow upwards out cylinder, are taken away by river bottom flowing water, so follow
Ring achievees the purpose that constantly to purify heavy metal in river bottom mud.
Cuboid bricked of the invention can be placed in river bottom mud always, be adsorbed by the osmosis of water in bed mud
Heavy metal in water.
Preferred scheme, scheme b middle column body and column cover and solid cone are made of stainless steel material.
Compared with the prior art, the technical solution bring advantageous effects of the present patent application:
(1) heavy metal in permanent absorption bed mud or in water can be continued, the content of heavy metal in bed mud can be greatly reduced.
(2) without cofferdam, the highly difficult construction such as shut off, river bed sludge is not disturbed, does not influence the river water water in layout points downstream
Matter.Bed mud ecologic stability is not influenced, does not destroy river ecosystem；Material, which is arranged in, will not influence the normal of river in river
Current and river surface operation.
(3) heavy metal in river bottom mud can be not only removed, and heavy metal can be recycled, resource is made to obtain abundant benefit
With；Nano-porous ceramic material is renewable simultaneously, and recycling greatly reduces processing cost.
(4) implement convenience, it is at low cost, it is not required to take over the land for use on riverbank periphery and builds Large Construction place, be suitable for all types of rivers
Fluid stream channel bed mud is administered.
(5) the nano-porous ceramic composite material adsorption capacity selected is big, selectivity is good, and stability is good, is used for a long time
Harmful components are not discharged, any side effect will not be brought to bed mud, do not influence the balance system of river water body, and material is recyclable
Regeneration.
Detailed description of the invention
[Fig. 1] is the schematic diagram that embodiment 1 handles river bottom mud heavy metal using heavy metal adsorption column B；
[Fig. 2] is process flow chart of the invention；
[Fig. 3] is the schematic diagram that embodiment 2 handles river bottom mud heavy metal using heavy metal adsorption column A；
[Fig. 4] is the schematic diagram that embodiment 3 handles river bottom mud heavy metal using heavy metal brick；
[Fig. 5] is heavy metal adsorption column A sectional view；
[Fig. 6] is heavy metal adsorption column B sectional view；
[Fig. 7] is cuboid bricked sectional view made of nano-porous ceramic composite material；
[Fig. 8] is the sectional view of nano-porous ceramic composite material；
1 is the solid cone of metal adsorption column A, and 2 be the hollow cylinder of metal adsorption column A, and 3 be nano-porous ceramic
Composite material, 4 be netted stainless steel cover, 5 be metal adsorption column A cavity, 6 be heavy metal adsorption column B solid cone, 7
It is nano-porous ceramic composite material granular for movable clamp groove, 8,9-1 is hollow prism scapus cover, and 9-2 is hollow circuit cylinder scapus
Cover, 10 be aperture, and 11-1 is the outer hollow prism body of heavy metal adsorption column B, and 11-2 is the outer hollow circuit cylinder of heavy metal adsorption column B
Body, 12-1 are the interior hollow prism body of heavy metal adsorption column B, and 12-2 is the interior hollow cylinder of heavy metal adsorption column B, and 13 be close
Seal inner cover；The cavity of 14 heavy metal adsorption column B cylinders, 15 be nano-porous ceramic, and 16 be organic small point containing active function groups
Sublayer, 17 be nano-pore.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Fig. 5 is heavy metal adsorption column A；It is made by nano-porous ceramic composite material 3 (MA01, MF01, MP02 or MP01)
At hollow cylinder 2 is made in upper side, and solid cone 1 is made in lower part, and lower part solid cone 1 is mainly planted convenient for equipment
Enter river bottom mud, while there is the absorption huge sum of money function of dominant.Top is arranged to hollow cylinder 2, and top is equipped with netted stainless steel
Lid 4, external water can be penetrated into 2 internal cavities 5 of hollow cylinder by 2 post jamb of hollow cylinder, pass through netted stainless steel cover
Outflow；Nano-porous ceramic composite material 3 is carrier, the surface of nano-porous ceramic 15 and internal packet with nano-porous ceramic 15
Containing nano-pore 17 abundant, the intensive regular small organic molecule layer 16 being modified with containing active function groups of 17 inner surface of nano-pore.In
2 outer diameter of hollow cylinder is 0.10~0.30 meter, and internal diameter is 0.02~0.10 meter, and a length of 0.5~2.0 meter, solid cone 1 is a height of
0.02~0.30 meter；Entire heavy metal adsorption column A is made of 5~30 kilograms of nano-porous ceramic composite materials 3.
Fig. 6 is heavy metal adsorption column B；Including the column cover and lower part solid cone 6 outside top cylinder and cylinder.
Top cylinder and lower part solid cone 6 are made of stainless steel material, and 6 a height of 0.02~0.30 meters of solid cone, mainly just
It plants and is fixed in river bottom mud in equipment.The top cylinder can constitute (Fig. 6-A institute by inside and outside double layer hollow prism
Show), area filling has nano-porous ceramic composite material granular between outer hollow prism body 11-1 and interior hollow prism body 12-1
8,8 large specific surface area of nano-porous ceramic composite material granular, adsorption efficiency are high；Outer hollow prism body 11-1 and interior hollow prism
Be intensively distributed on the post jamb of body 12-1 aperture be 1~1.5 millimeter of aperture 10, outer hollow prism body 11-1 side length be 0.02~
0.25 meter, the outer hollow prism body 11-1 side length of interior hollow prism body 12-1 side ratio is 0.01~0.15 meter short, interior hollow prism body
12-1 and outer hollow prism body 11-1 high is 0.5~2.0 meter；Column cover 9-1 is hollow prism body, and column cover 9-1 is by stainless steel
Material is made, and the outer hollow prism body 11-1 side length of side ratio is 0.03~0.05 meter long, high with interior hollow prism body 12-1 and outer hollow
Prism 11-1 high is consistent.Alternatively, the top cylinder is made of inside and outside double layer hollow cylindrical body (shown in Fig. 6-B), it is outer in
Between hollow cylinder 11-2 and interior hollow cylinder 12-2 area filling have nano-porous ceramic composite material granular 8 (MA01,
MF01, MP02 or MP01)；Being intensively distributed with aperture on the post jamb of outer hollow cylinder 11-2 and interior hollow cylinder 12-2 is
1~1.5 millimeter of aperture 10；Outer hollow circuit cylinder 11-2 diameter is 0.02~0.25 meter, and interior hollow cylinder 12-2 diameter is than in outer
Hollow round column 11-2 diameter is 0.03~0.20 meter short, and interior hollow circuit cylinder cylinder 12-2 and outer hollow cylinder 11-2 high be 0.5~
2.0 rice；Column cover 9-2 is hollow cylinder, and column cover 9-2 is made of stainless steel material, and diameter is than outer hollow cylinder 11-2 diameter
It is 0.03~0.05 meter long, it is high consistent with interior hollow cylinder 12-2 and outer hollow cylinder 11-2 high.Have in sealing at the top of cylinder
Lid 13, inner sealing lid 13 prevent bed mud enter between outer hollow prism body 11-1 and interior hollow prism body 12-1 region or it is outer in
Region between hollow cylinder 11-2 and interior hollow cylinder 12-2；Nano-porous ceramic composite material granular 8 can use mesh bag
It is distributed into pouch, the region being filled between outer hollow prism body 11-1 and interior hollow prism body 12-1 or outer hollow cylinder
Region between 11-2 and interior hollow cylinder 12-2.Loading is 2~30 kilograms of nano-porous ceramics in heavy metal adsorption column B
Composite material granular 8；Cylinder and the bottom (9-2) column cover 9-1 are connect with 6 underrun movable clamp groove 7 of solid cone, are conducive to
Column cover 9-1 (9-2) installation and dismounting.
Fig. 7 is the cuboid brick being made of nano-porous ceramic composite material 3 (MA01, MF01, MP02 or MP01).It is long
Cube block dimensions size is 5~30cm × 3~25cm × 1~10cm；Every piece of cuboid bricked nano-porous ceramic composite wood
Material weighs 0.2~3 kilogram.
Embodiment 1
Heavy metal cadmium content is 5.8mg/kg in A sections of East Hunan river bed mud；Zn content is 792.2mg/kg；Copper contains
Amount is 263.1mg/kg.
Two-tier rhombic cylinder equipment is selected, water chestnut bar shape outer cover side length is 0.2 meter, the outer side length 0.16 of lining material layer
Rice, 0.06 meter of interior side length, inside and outside wall open pore size are 1.2 millimeters, and cylinder length is 1m, lower part solid cone height 0.15
Rice, built-in material MA01 amount are 10kg.Often it is separated by 3 meters of one root timber stock columns of insertion in bed mud in river, takes outer cover, lining material away
Column capital is higher by bed mud surface layer 0.1m.
By 4 months period treatments, the heavy metal cadmium content detected in bed mud in river was reduced to 3.3mg/kg；Zn content
It is reduced to 472.3mg/kg；Copper content is reduced to 183.6mg/kg.A huge sum of money by extending several process cycles, in river bottom mud
The removal rate for belonging to cadmium, zinc and copper reaches 85% or more.
The multi-metal ion of MA01 absorption reaches saturation, and the EDTA solution that can be 2.5wt% with concentration by MA01 is washed
After de-, recycling heavy metal cadmium, zinc and copper, the adsorption capacity after MA01 regeneration reach the 95% of original material, reusable, such as
The heavy metal ion amount of absorption is not up to saturated, and can be continued to use.
Embodiment 2
Heavy metal cadmium content is 8.7mg/kg in B sections of East Hunan river bed mud；Zn content is 668.9mg/kg；Copper contains
Amount is 233.6mg/kg.
The selection of material column equipment, nano-porous ceramic composite material MA01 amount are 15 kilograms, column of material cylinder diameter
It is 0.2 meter, length is 1.0 meters, and internal diameter is 0.08 meter, and bottom cone height is 0.15 meter.Material cylindrical body is inserted perpendicularly into river
In road bed mud, every pillar is separated by 2 meters, and every root cutting is higher by 0.1 meter of bed mud surface layer after entering bed mud.
By 12 months period treatments, the heavy metal cadmium content detected in bed mud in river was reduced to 4.5mg/kg；Zinc contains
Amount is reduced to 332.6mg/kg；Copper content is reduced to 150.9mg/kg.Weight by extending several process cycles, in river bottom mud
The removal rate of cadmium metal, zinc and copper reaches 85% or more.
The multi-metal ion of MA01 absorption reaches saturation, and the EDTA solution that can be 1.5wt% with concentration by MA01 is washed
After de-, recycling heavy metal cadmium, zinc and copper, the adsorption capacity after MA01 regeneration reach the 95% of original material, reusable, such as
The heavy metal ion amount of absorption is not up to saturated, and can be continued to use.
Embodiment 3
Heavy metal cadmium content is 4.0mg/kg in C sections of East Hunan river bed mud；Zn content is 682.7mg/kg；Copper contains
Amount is 221.8mg/kg.
The selection of material brick equipment, every piece of cuboid bricked nano-porous ceramic composite material MA01 and MP01 (quality 1:1)
2 kilograms are weighed, is embedded to 4 blocks of nano-porous ceramic composite materials in average every square metre of river bottom mud, depth is at 40 centimetres.
To the period treatment for passing through 12 months, the heavy metal cadmium content detected in bed mud in river is reduced to 1.7mg/kg；Zinc
Content is reduced to 320.2mg/kg；Copper content is reduced to 113.5mg/kg.By extending several process cycles, in river bottom mud
The removal rate of heavy metal cadmium, zinc and copper reaches 85% or more.
If the multi-metal ion of MA01 absorption reaches saturation, MA01 can be eluted with the hydrochloric acid that concentration is 10wt%
Afterwards, heavy metal cadmium, zinc and copper are recycled, the adsorption capacity after MA01 regeneration reaches the 90% of original material, and it is reusable, if
The heavy metal ion amount of absorption is not up to saturated, and can be continued to use.
Embodiment 4
The regeneration tests of nano-porous ceramic material:
MA01, MF01, MP02 or MP01 can be regenerated with EDTA and HCl, wherein using material adsorption capacity after EDTA regeneration
It can restore to initial 95%, the use of material adsorption capacity after regeneration of hydrochloric acid be initial 50%.After increase vacuumizes, it can restore
To the 70% of initial capacity.Experiment flow and data are as follows:
Experiment equipment and reagent:
Using test explanation is carried out for MA01 porous ceramic film material, prepared 200ppm waste water containing Cd；
250mL triangular flask, 250mL beaker, 250mL graduated cylinder, 10mL pipette, dropper vibrate case, assay balance etc.；
1, experimental procedure:
1) 30 parts of MA012.00g, are accurately weighed respectively with assay balance in 30 cleaned 250mL triangular flasks, point
It 1. 2. 3. Bian Hao not be ...；
2) waste water containing Cd that 100mL prepared 200ppm, is measured with clean 250mL graduated cylinder, in 1 triangular flask,
Successively install 30 triangular flasks；
3), 2 triangular flask is put into oscillation case and is vibrated, revolving speed 130rpm, temperature is room temperature (21 DEG C or so), oscillation
2h；
4) 10mL in the test tube for, taking 3 water sample in being composed of 1. 2. 3. ..., remaining heavy metal-containing waste water pour into Sewage treatment
Bucket, as far as possible to the greatest extent, sample inspection；
5), 10.0mL 6mol/L HCl or 1.5%EDTA solution is taken with the pipette of 10mL (take and separate when different liquids)
Respectively in the MA01 triangular flask being added after adsorbing, being placed in oscillation case, 130rpm, room temperature (21 DEG C or so) vibrates 1h；
6), the regenerated liquid in the above-mentioned triangular flask of oscillation is poured at wastewater collection, as far as possible to the greatest extent；
7) regenerated material in triangular flask, is cleaned with clear water, is respectively washed 5 times, then 1 time wash with distilled water, is vacuumized；
8) adsorption test again, is carried out, repeats 2~8；
Note: 1, the above experiment is completed in three batches；2, Cd solution used is matching while using, every batch of absorption in experimentation
Cd solution used is same, and while measuring every time measures the concentration of matched Cd solution simultaneously；
Test junction fruit and analysis
By testing to obtain data such as the following table 7 above:
Unit: mg/L
Absorption and desorption test data table of the 7 MA01 porous ceramic film material of table to heavy metal cadmium
Note: A1 is solution C d concentration after adsorbing for the first time, Cd concentration in regenerated liquid after R1 regenerates for first time,
And so on.
It performs an analysis to upper table data, calculates adsorbance and desorption rate, obtain result as shown in table 8 below.
Absorption and desorption test effect data of the 8 MA01 porous ceramic film material of table to heavy metal cadmium
2. test result analysis
First time adsorption effect reaches as high as 79%, minimum 37%, and average 57%；
In regeneration, EDTA effect preferably can reach 95%；
HCl effect is general, and the adsorbance in regenerative process is about the 50% of first time.
Claims (5)
1. a kind of method in situ for administering river bottom mud heavy metal, it is characterised in that: including a or c scheme:
Scheme a: by heavy metal adsorption column A by being spaced in 1~4 meter of implantation river bottom mud in length and breadth, implantation depth is that column cap is higher by river
0.05~0.30 meter of road bed mud surface layer carries out adsorption treatment to heavy metal ion in river bottom mud；
The heavy metal adsorption column A is made of upper hollow cylindrical body and lower part solid cone, hollow cylinder and solid
Cone is made of nano-porous ceramic composite material；Each heavy metal adsorption column A is compound by 5~30 kilograms of nano-porous ceramics
Material is made；
Scheme c: (5~30) cm × (3~25) cm × (1~10) cm cuboid brick is made in nano-porous ceramic composite material
Block is uniformly embedded in river bottom mud, carries out adsorption treatment to heavy metal in river bottom mud；The nanoporous of every piece of cuboid brick
Ceramic composite weighs 0.2~3 kilogram, and 2~10 kilograms of nano-porous ceramics of embedment are compound in average every cubic metre of river bottom mud
Material；
The nano-porous ceramic composite material is at least one of MA01, MF01, MP02 and MP01；
The method for recycling heavy metal is to wash the nano-porous ceramic composite material for having adsorbed heavy metal by EDTA solution
It is de-, recycle heavy metal.
2. the method in situ for administering river bottom mud heavy metal according to claim 1, it is characterised in that: in scheme a
Hollow cylinder outer diameter is 0.10~0.30 meter, and internal diameter is 0.02~0.10 meter, and a length of 0.5~2.0 meter, solid cone is a height of
0.02~0.30 meter.
3. the method in situ for administering river bottom mud heavy metal according to claim 1, it is characterised in that: in scheme a
Netted stainless steel cover is equipped at the top of hollow cylinder.
4. the method in situ for administering river bottom mud heavy metal according to claim 1, it is characterised in that: scheme a or scheme c
Process cycle is 1~12 month.
5. the method in situ for administering river bottom mud heavy metal according to claim 1, it is characterised in that: described in scheme a
Heavy metal adsorption column A in river bottom mud heavy metal adsorption handle a period after, take out nano-porous ceramic composite material, return
Receive heavy metal；In scheme c, cuboid bricked nano-porous ceramic composite material handles heavy metal adsorption in river bottom mud one week
After phase, nano-porous ceramic composite material is taken out, heavy metal or without any processing is recycled, heavy metal is fixed on river
Inside bed mud.
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| CN109455890B (en) * | 2018-11-05 | 2023-09-22 | 河海大学 | Polluted bottom mud in-situ covering net without disturbance of floating mud and paving method thereof |
| CN113845281B (en) * | 2021-10-27 | 2023-07-18 | 杭州民安环境工程有限公司 | In-situ repair method for bottom mud |
Citations (3)
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|---|---|---|---|---|
| RU2125542C1 (en) * | 1996-04-03 | 1999-01-27 | Николай Никифорович Дыханов | Method of reusing waste water sludges containing mixtures of heavy metal hydroxides and/or hydroxocarbonates |
| CN103526719A (en) * | 2013-10-22 | 2014-01-22 | 江苏江达生态科技有限公司 | Repair technology for river and lake bottom mud site polluted by heavy metal |
| CN204737751U (en) * | 2015-04-13 | 2015-11-04 | 国佳新材湖北环保凝胶产业园有限公司 | Gel moves heavy metal ion removal device of structuring formation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2125542C1 (en) * | 1996-04-03 | 1999-01-27 | Николай Никифорович Дыханов | Method of reusing waste water sludges containing mixtures of heavy metal hydroxides and/or hydroxocarbonates |
| CN103526719A (en) * | 2013-10-22 | 2014-01-22 | 江苏江达生态科技有限公司 | Repair technology for river and lake bottom mud site polluted by heavy metal |
| CN204737751U (en) * | 2015-04-13 | 2015-11-04 | 国佳新材湖北环保凝胶产业园有限公司 | Gel moves heavy metal ion removal device of structuring formation |
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