CN104726104B - The preparation method of heavy-metal contaminated soil improvement modified mineral composition - Google Patents

The preparation method of heavy-metal contaminated soil improvement modified mineral composition Download PDF

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CN104726104B
CN104726104B CN201510142706.6A CN201510142706A CN104726104B CN 104726104 B CN104726104 B CN 104726104B CN 201510142706 A CN201510142706 A CN 201510142706A CN 104726104 B CN104726104 B CN 104726104B
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mineral
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soil improvement
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CN104726104A (en
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梁丽芹
沈培友
杭小帅
马国超
曹康
曹一康
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OUBAITE CLAY MATERIAL CO Ltd XUYI
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/08Aluminium compounds, e.g. aluminium hydroxide
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a kind of heavy-metal contaminated soil improvement preparation method of modified mineral composition, comprise the following steps:By attapulgite, vermiculite, sepiolite, zeolite, diatomite difference coarse crushing and roller screen, five kinds of little particle mineral under sieving are uniformly mixed, obtain mixed mineral, spray water to mixed mineral, is then squeezed into shaped minerals composition;The shaped minerals composition is stacked, is dried naturally;Input rotary kiln is roasted, the mineral after being roasted;Mineral after the roasting and flyash, quick lime are compounded, are mixed, obtain mixture;The mixture is milled, to obtain the final product.On the one hand modifying agent composition provided by the invention is acted on by the absorption to heavy metal, precipitation etc., change the existence of heavy metal in the soil, reduce the biological effectiveness and migration of heavy metal;On the other hand, by improving soil texture, the water-retaining property and gas permeability of soil is improved, may advantageously facilitate plant growth.

Description

The preparation method of heavy-metal contaminated soil improvement modified mineral composition
Technical field
The present invention relates to a kind of preparation method of contaminated soil conditioner composition, and in particular to a kind of heavy metal polluted soil The preparation method of earth improvement modified mineral composition.
Background technology
The strategic resource that soil is human survival, is made the country prosperous and stable.With industrialization, urbanization, intensive agriculture it is quick Development, a large amount of undressed discarded objects are shifted to soil system, and are collected under the action of natural cause, residued in soil ring In border.It is estimated that China is reached up to ten million hectares by the contaminated soil such as pesticide, heavy metal area, to China's ecological environment matter Amount, food security and social economy's sustainable development constitute a serious threat.The species of polluter mainly have heavy metal, nitrate, Pesticide and persistence organic pollutant, radionuclide, pathogen/virus and xenobiotic etc..At present, Soil pollution degradation Multi-source, modern environment contamination characteristics that are compound, measuring big, wide, lasting murder by poisoning have been shown, have just been turned to from constant pollutant micro- Measure persistence and poison pollutant, especially in rapidly developing region, the overall present situation of Soil pollution degradation is from Local immunotherapy To region, rural area is extended to from city outskirts of a town, combined pollution is expanded to from Single Pollution, be developed to from poisonous and harmful pollution poisonous Harmful pollution intersects with what N, P nutrition were polluted, forms point source and is coexisted with pollution of area source, domestic pollution, agricultural pollution and industry are dirty Dye superposition, various new and old pollutions and secondary pollution be mutual compound or the situation that mixes.
Soil pollution brings extremely serious consequence:First, soil pollution makes natively nervous cultivated land resource more Shortage;Second, soil pollution brings great threat to the health of the people;3rd, soil pollution is brought to agricultural development Very big adverse effect;4th, soil pollution is also to cause the major reason of other environmental pollutions;5th, in soil pollution Pollutant has migration and anelasticity, it is possible to continues to cause new land pollution;6th, soil pollution seriously jeopardizes offspring The interests of descendants, are unfavorable for the sustainable development of rural economy.Therefore, the modification method for studying contaminated soil has important meaning Justice.At present, for the improvement of heavy-metal contaminated soil, mainly by it is biological prosthetic, use lime, applying organic manure, tune of pouring water The measures such as soil pH value, passenger's soil are saved to reduce or eliminate pollution, effect also respectively has quality, such as biological restoration removing heavy metals Effect is preferable, but the early period of biological agent, manufacture was of high cost, also restricted its application range.
CN103351870A (publication date 2013-10-16) discloses a kind of soil conditioner, including following weight ratio is each Component:Acrylamide and acrylic acid salt crosslinking copolymerization thing 10-15, acrylamide and acrylic acid receive copolymer 20-30, montmorillonite 55- 60, and formed by each component chelating.This soil conditioner is pale yellow powder particle, it mixes anti-through granule with soil Should and hydrophobic reactant after formed there is very loose crumb structure soil, the crumb structure soil with excellent fertilizer conservation, Water conservation, ventilative solid-liquid-gas three phase structure, beneficial to the growth of root system of plant.
Although above-mentioned improvement and modification method prior art discloses some heavy-metal contaminated soils, disclosure satisfy that certain Needs, but these technologies still suffer from the defects of certain:It is of high cost for example the removal effect of heavy metal is undesirable, it is not suitable for big Scale promotes and applies.
Therefore, there is further improvement and optimization and need in the administering method for heavy-metal contaminated soil in the prior art Ask, this is also one of research hotspot and emphasis in the technical field, is even more power and starting point institute that the present invention is accomplished .
The content of the invention
In order to overcome improvement of contaminated soil existing in the prior art of high cost and the undesirable skill of the removal effect of heavy metal Art problem, the present inventor is after substantial amounts of further investigation has been carried out, so as to complete the present invention.
The present invention is achieved through the following technical solutions, and is modified in particular to a kind of heavy-metal contaminated soil improvement The preparation method of mineral composition, comprises the following steps:
Step (1), distinguishes coarse crushing and roller screen by attapulgite, vermiculite, sepiolite, zeolite, diatomite, five kinds under sieving Little particle mineral are uniformly mixed, and obtain mixed mineral, spray water to mixed mineral, is then squeezed into shaped minerals composition;
Step (2), by the shaped minerals composition stack 48 it is small when more than, be then dried to moisture weight content naturally Less than 20%;
Step (3), shaped minerals composition input rotary kiln of the moisture weight content less than 20% is roasted, Mineral after being roasted;
Step (4), the mineral after the roasting and flyash, quick lime are compounded, are mixed, and obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
Preferably, in step (1), the aperture of the roller screen is 2-5cm, which, which includes, belongs to any tool therein Body point value, such as 2cm, 3cm, 4cm or 5cm, most preferably 3cm, also include any two point value institute in these specific point values The scope of composition, more preferably 3-4cm.
Preferably, in step (1), in five kinds of little particle mineral, the convex Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ diatoms of Ao The weight ratio of soil is (5-8):(1-2):(1-2):(1-2):(1-2), the scope include belong to it is therein any specific Value, such as 5 ︰, 1 ︰, 1 ︰, 11 ︰ of ︰ 1,6 ︰, 1 ︰, 11 ︰ of ︰ 1,7 ︰, 1 ︰, 11 ︰ of ︰ 1,8 ︰, 1 ︰, 12 ︰ of ︰ 1,5 ︰, 2 ︰, 22 ︰ of ︰ 2,6 ︰, 2 ︰, 22 ︰ of ︰ 2,7 ︰, 2 ︰, 2 ︰ 2, 8 ︰, 2 ︰, 2 ︰, 22 ︰ of ︰ 2,5 ︰, 1 ︰, 11 ︰ of ︰ 2,6 ︰, 2 ︰, 22 ︰ of ︰ 2,7 ︰, 1 ︰, 1 ︰ 2 or 8 ︰, 2 ︰, 1 ︰, 1 ︰ 1 of 2 ︰ 2,1 ︰ of most preferably 6 ︰, 1 ︰, also include this The scope that any two point value in a little specific point values is formed, more preferably 1 ︰ of (5-8) ︰, 1 ︰, 1 ︰ 1.
Preferably, in step (1), sprinkling underground water to mixed mineral.
Preferably, in step (1), spray water to mixed mineral makes, and the moisture weight content of mixed mineral is 40-50%, The scope, which includes, belongs to any specific point value therein, for example, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%th, 48%, 49% or 50%, most preferably 45%, also include what any two point value in these specific point values was formed Scope, more preferably 43-48%.
Preferably, in step (1), shaped minerals composition is squeezed into using three-roller.
Preferably, in step (1), 1-5mm, the scope include the lamellar spacing of the shaped minerals composition in order to control Any specific point value therein, such as 1mm, 2mm, 3mm, 4mm or 5mm are belonged to, most preferably 3mm, it is specific to also include these The scope that any two point value in point value is formed, more preferably 2-4mm.
Preferably, in step (3), the temperature of the roasting is 540-560 DEG C, which, which includes, belongs to therein What specific point value, such as 540 DEG C, 542 DEG C, 545 DEG C, 547 DEG C, 550 DEG C, 553 DEG C, 555 DEG C, 557 DEG C or 560 DEG C, also include The scope that any two point value in these specific point values is formed, more preferably 545-555 DEG C.
Preferably, in step (3), time 10-20 minute of the roasting, the scope include belong to it is therein any Specific point value, for example, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, also include the scope that any two point value in these specific point values is formed, more preferably 13-18 minutes.
Preferably, in step (3), shaped minerals composition of the moisture weight content less than 20% is inputted with conveyer belt Rotary kiln.
Preferably, in step (4), the weight ratio of mineral, flyash, quick lime after roasting is (1-3):(1-3):(1- 2), which, which includes, belongs to any specific point value therein, such as 1 ︰, 1 ︰ 1,1 ︰, 2 ︰ 2,1 ︰, 3 ︰ 1,1 ︰, 3 ︰ 2,3 ︰, 1 ︰ 1,3 ︰ 1 ︰ 2,3 ︰, 3 ︰ 1,2 ︰ 2 ︰ 1 or 3 ︰ 2 ︰ 1 of 3 ︰ 2, most preferably 2 ︰, any two point value also included in these specific point values are formed Scope, more preferably (1-2):(1-2):(1-2).
Compared with prior art, beneficial effects of the present invention are as follows:The present invention by the selections of five kinds of raw mineral materials and The complex optimum of the series of steps such as crushing, tabletting, roasting, compounding and milling, especially roasts the effect of link so that offer Modifying agent composition on the one hand by the absorption to heavy metal, precipitation etc. effect, change heavy metal in the soil there are shape State, reduces the biological effectiveness and migration of heavy metal;On the other hand, by improving soil texture, the guarantor of soil is improved Water-based and gas permeability, may advantageously facilitate plant growth.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiments will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1
The present embodiment is related to a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition, by following step Rapid composition:
Step (1), distinguishes coarse crushing, aperture 5cm roller screens, by under sieve by attapulgite, vermiculite, sepiolite, zeolite, diatomite Five kinds of little particle mineral (the convex diatomaceous weight ratios of Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ of Ao are 6 ︰, 1 ︰, 1 ︰, 1 ︰ 1) mixing it is equal It is even, mixed mineral is obtained, sprinkling underground water to mixed mineral, the moisture weight content for making mixed mineral is 48%, is then used Three-roller is squeezed into shaped minerals composition (control lamellar spacing 5mm);
Step (2), by the shaped minerals combination stack 48 it is small when more than, be then dried to that moisture weight content is small naturally In 20%;
Step (3), rotary kiln is inputted by the moisture weight content conveyer belt of the shaped minerals composition less than 20%, 540 DEG C of temperature is controlled, is roasted, is stopped about 13 minutes, the mineral after being roasted;
Step (4), the mineral after roasting are compounded with flyash, quick lime according to 2 ︰ of weight ratio, 2 ︰ 1, are mixed, are obtained Obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
Embodiment 2
The present embodiment is related to a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition, by following step Rapid composition:
Step (1), distinguishes coarse crushing, aperture 4cm roller screens, by under sieve by attapulgite, vermiculite, sepiolite, zeolite, diatomite Five kinds of little particle mineral (the convex Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ diatomite of Ao is 8 ︰, 1 ︰, 1 ︰, 1 ︰ 1) be uniformly mixed, mixed Mineral are closed, sprinkling underground water to mixed mineral, the moisture weight content for making mixed mineral is 50%, is then extruded using three-roller Slabbing mineral composition (control lamellar spacing 1mm);
Step (2), by the shaped minerals combination stack 48 it is small when more than, be then dried to that moisture weight content is small naturally In 20%;
Step (3), rotary kiln is inputted by the moisture weight content conveyer belt of the shaped minerals composition less than 20%, 545 DEG C of temperature is controlled, is roasted, is stopped about 15 minutes, the mineral after being roasted;
Step (4), the mineral after roasting are compounded with flyash, quick lime according to 1 ︰ of weight ratio, 1 ︰ 1, are mixed, are obtained Obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
Embodiment 3
The present embodiment is related to a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition, by following step Rapid composition:
Step (1), distinguishes coarse crushing, aperture 3cm roller screens, by under sieve by attapulgite, vermiculite, sepiolite, zeolite, diatomite Five kinds of little particle mineral (the convex diatomaceous weight ratios of Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ of Ao are 5 ︰, 2 ︰, 2 ︰, 2 ︰ 2) mixing it is equal It is even, mixed mineral is obtained, sprinkling underground water to mixed mineral, the moisture weight content for making mixed mineral is 40%, is then used Three-roller is squeezed into shaped minerals composition (control lamellar spacing 2mm);
Step (2), by the shaped minerals combination stack 48 it is small when more than, be then dried to that moisture weight content is small naturally In 20%;
Step (3), rotary kiln is inputted by the moisture weight content conveyer belt of the shaped minerals composition less than 20%, 550 DEG C of temperature is controlled, is roasted, is stopped about 18 minutes, the mineral after being roasted;
Step (4), the mineral after roasting are compounded with flyash, quick lime according to 1 ︰ of weight ratio, 3 ︰ 1, are mixed, are obtained Obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
Embodiment 4
The present embodiment is related to a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition, by following step Rapid composition:
Step (1), distinguishes coarse crushing, aperture 2cm roller screens, by under sieve by attapulgite, vermiculite, sepiolite, zeolite, diatomite Five kinds of little particle mineral (the convex diatomaceous weight ratios of Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ of Ao are 5 ︰, 1 ︰, 2 ︰, 1 ︰ 2) mixing it is equal It is even, mixed mineral is obtained, sprinkling underground water to mixed mineral, the moisture weight content for making mixed mineral is 43%, is then used Three-roller is squeezed into shaped minerals composition (control lamellar spacing 3mm);
Step (2), by the shaped minerals combination stack 48 it is small when more than, be then dried to that moisture weight content is small naturally In 20%;
Step (3), rotary kiln is inputted by the moisture weight content conveyer belt of the shaped minerals composition less than 20%, 555 DEG C of temperature is controlled, is roasted, is stopped about 20 minutes, the mineral after being roasted;
Step (4), the mineral after roasting are compounded with flyash, quick lime according to 1 ︰ of weight ratio, 3 ︰ 2, are mixed, are obtained Obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
Embodiment 5
The present embodiment is related to a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition, by following step Rapid composition:
Step (1), distinguishes coarse crushing, aperture 3cm roller screens, by under sieve by attapulgite, vermiculite, sepiolite, zeolite, diatomite Five kinds of little particle mineral (the convex diatomaceous weight ratios of Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ of Ao are 7 ︰, 1 ︰, 2 ︰, 1 ︰ 2) mixing it is equal It is even, mixed mineral is obtained, sprinkling underground water to mixed mineral, the moisture weight content for making mixed mineral is 45%, is then used Three-roller is squeezed into shaped minerals composition (control lamellar spacing 4mm);
Step (2), by the shaped minerals combination stack 48 it is small when more than, be then dried to that moisture weight content is small naturally In 20%;
Step (3), rotary kiln is inputted by the moisture weight content conveyer belt of the shaped minerals composition less than 20%, 560 DEG C of temperature is controlled, is roasted, is stopped about 10 minutes, the mineral after being roasted;
Step (4), the mineral after roasting are compounded with flyash, quick lime according to 3 ︰ of weight ratio, 1 ︰ 2, are mixed, are obtained Obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
Comparative example 1
This comparative example and embodiment 1 difference lies in:Step (3) is omitted, i.e., without high-temperature roasting.
Comparative example 2
This comparative example and embodiment 2 difference lies in:Step (3) is omitted, i.e., without high-temperature roasting.
Comparative example 3
This comparative example and embodiment 3 difference lies in:Step (3) is omitted, i.e., without high-temperature roasting.
Comparative example 4
This comparative example and embodiment 4 difference lies in:Step (3) is omitted, i.e., without high-temperature roasting.
Comparative example 5
This comparative example and embodiment 5 difference lies in:Step (3) is omitted, i.e., without high-temperature roasting.
Implement above-described embodiment 1-5 and comparative example 1-5 respectively and then obtain modified mineral composition sample, will be heavy metal-polluted Soil is contaminated with above-mentioned modified mineral composition sample according to weight ratio 100:3 carry out the removal of heavy metal-polluted soil (cadmium) at normal temperatures Improved test, heavy-metal contaminated soil used in each experiment pick up from same area, and the sample of each embodiment and comparative example repeats Five improved tests, take its average value to be calculated and counted, acquired results are as shown in table 1 below.
The result of table 1 embodiment 1-5 and comparative example 1-5
As seen from the above table, the cadmium removal rate in embodiment 1-5 is in 93.3-97.2%, and the cadmium removal rate of comparative example 1-5 exists 67.8-71.6%, illustrates that the removing amplitude of embodiment 1-5 Heavy Metals in Contaminated Soils cadmiums is notable, further illustrates in step (3) Effect of the high-temperature roasting technique for the modified mineral composition that finally obtains in terms of Heavy Metals in Soil Contaminated improves removal It it is 540-560 DEG C with vital influence, especially calcination temperature, what the time of roasting obtained when being 10-20 minutes changes Property mineral composition it is more prominent in the removal effect of soil heavy metal cadmium.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (10)

1. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition, it is characterised in that including following step Suddenly:
Step (1), distinguishes coarse crushing and roller screen by attapulgite, vermiculite, sepiolite, zeolite, diatomite, five kinds small under sieving Grain mineral are uniformly mixed, and obtain mixed mineral, spray water to mixed mineral, is then squeezed into shaped minerals composition;
Step (2), by the shaped minerals composition stack 48 it is small when more than, be then dried to that moisture weight content is less than naturally 20%;
Step (3), shaped minerals composition input rotary kiln of the moisture weight content less than 20% is roasted, is obtained Mineral after roasting;
Step (4), the mineral after the roasting and flyash, quick lime are compounded, are mixed, and obtain mixture;
Step (5), the mixture is milled, up to soil improvement modified mineral composition.
2. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (1), the aperture of the roller screen is 2-5cm.
3. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (1), in five kinds of little particle mineral, and the convex diatomaceous weight of Bang Shi ︰ Zhi Shi ︰ Hai Pao Shi ︰ Fei Shi ︰ of Ao Than for (5-8):(1-2):(1-2):(1-2):(1-2).
4. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (1), sprinkling underground water to mixed mineral.
5. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (1), spray water to mixed mineral makes the moisture weight content of mixed mineral be 40-50%.
6. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (1), shaped minerals composition is squeezed into using three-roller.
7. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (1), the lamellar spacing of shaped minerals composition 1-5mm in order to control.
8. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (3), the temperature of the roasting is 540-560 DEG C.
9. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (3), time 10-20 minute of the roasting.
10. a kind of preparation method of heavy-metal contaminated soil improvement modified mineral composition as claimed in claim 1, it is special Sign is, in step (4), the weight ratio of mineral, flyash, quick lime after roasting is (1-3):(1-3):(1-2).
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粘土矿物修复重金属污染土壤;杭小帅等;《环境工程学报》;20070905;第1卷(第9期);第115-116页"改性粘土矿物的特性及其应用" *

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