CN104263374B - A kind of soil heavy metal combined stabilizer and its application method - Google Patents
A kind of soil heavy metal combined stabilizer and its application method Download PDFInfo
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- CN104263374B CN104263374B CN201410486233.7A CN201410486233A CN104263374B CN 104263374 B CN104263374 B CN 104263374B CN 201410486233 A CN201410486233 A CN 201410486233A CN 104263374 B CN104263374 B CN 104263374B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a kind of soil heavy metal combined stabilizer and its application method, wherein, the soil heavy metal combined stabilizer, by mass percentage, including following components：Organic substance 50% 80%, phosphate fertilizer 16% 40% and nitrogenous fertilizer 4% 16%.Soil heavy metal combined stabilizer application method is that the soil heavy metal combined stabilizer is well mixed into processing 15 days with the soil by heavy metal pollution in mass ratio 1: 5~8.Soil heavy metal combined stabilizer of the present invention, realize and organic matter, phosphate fertilizer and nitrogenous fertilizer are combined as improvement and ecological recovery of the stabilizer for heavy-metal contaminated soil, both the heavy metal in soil can be passivated stable, the effect of fertile soil can be reached again, the destruction to soil property is reduced as far as possible, is conducive to the recycling of soil.
Description
Technical field
The present invention relates to technical field of land improvement, it is mainly concerned with a kind of soil heavy metal combined stabilizer and its uses
Method.
Background technology
Soil is that the mankind depend on for existence the basis of activity, but environmental pollution and ecological disruption are increasingly serious, Qujing of Yunnan
Harm all reports common in recent years that the illegal dumping of chromium slag, cadmium rice event, blood lead event etc. are brought by heavy metal pollution, soil
Earth heavy metal pollution has become one of common problem for being received much attention in soil pollution.
Common remediation of heavy metal-contaminated soil mainly has a few major class sides such as physics, chemistry, biology, agricultural regulation
Method.Wherein, chemical passivation/technique for fixing have that applicability is wide, treating capacity big, instant effect, notable effect the features such as, thus obtain
It is extensive to use.At present, being commonly used for the material of heavy metal deactivator/stabilizer has natural clay mineral, organic matter, phosphorous thing
Matter, lime etc., by adjusting and changing physico-chemical property and form of the heavy metal in soil, are handed over using absorption, precipitation, ion
Change, the principle such as chelating/complexing, the heavy metal stable curing in soil is got off, so as to mitigate the biological effectiveness of heavy metal.But
It is that passivating technique still suffers from problems with：(1) stablizing effect of natural clay mineral heavy metal is slightly weak；(2) phosphorus containg substances have
There is certain selectivity, it is different to the passivation effect of different heavy metals in soil；(3) secondary pollution problem, such as phosphorus containg substances
Excessive addition easily cause the loss of phosphorus, bring secondary pollution；A large amount of use of lime causes soil hardening, destroys original reason
Change property etc..
Therefore, administering heavy-metal composite pollution soil need to select to each target contaminant effective passivator, according to not
The passivation effect and mechanism of same passivator heavy metal can strengthen single passivation material by being compounded to multiple material
The passivation of material, and reduce the environmental risk of secondary pollution.
Numerous studies show that organic matter is added into contaminated soil can be for the heavy metal in passivation soil.Often
There are green manure, lignite, cultivation excrement thing, organic compost, turf and crop material etc..As effective heavy metal complexing agent, have
Machine material can be by forming in insoluble petal-organic double compound, increase Cation Exchange Capacity in Soils (CEC), reduction soil
The water-soluble state and exchangeable species component of heavy metal, so as to reduce its plant availability.Bacteria residue (remaining culture after edible fungus culturing
Base) and natural decomposed cow dung in rich in the nutritional ingredient, the also microbiologic population with substantial amounts such as organic matter, nitrogen, phosphorus, potassium,
A large amount of carboxyls, hydroxyl, phosphoryl, phenolic group isoreactivity group are there is on the surface of bacteria residue and decomposed cow dung, with strong parent
Aqueous, adsorptivity, ion exchangeable etc., can occur ion exchange, absorption, complexing etc. instead with enlivening state heavy metal ion in soil
Should, so as to reduce the biological effectiveness of heavy metal ion.Bacteria residue is manufactured relative with application cost as a kind of agricultural solid waste
It is cheap, and wide material sources, there is larger application potential in terms of heavy-metal contaminated soil improvement.
Calcium superphosphate and ammonium sulfate are also current most common phosphate fertilizer and nitrogenous fertilizer.The heavy metal-passivated mechanism of phosphorus containg substances exists
Can be a variety of by occurring ion exchange, absorption, precipitation/co-precipitation, or even formation pyromorphite class mineral etc. with heavy metal in phosphorus
Form reduction P in soil b mobility and biological effectiveness.Ammonium sulfate is agriculturally commonly used to regulation soil as a kind of ammonium fertilizer
Earth pH, the active group (amino) that can be rich in by the use of it is used as the complexing such as ligand and heavy metal element Zn, Mn, Cu, Fe or chela
Close to weaken the biological effectiveness of heavy metal in soil.
In recent years, the edible fungus culturing of China more and more extensively change, scale, its concentrate large-scale production result be
Cause the edible fungi residue after harvesting largely to be discarded, its processing has become a difficult problem, and cause the ring that can not be ignored
Border problem.
The content of the invention
It is an object of the invention to provide a kind of soil heavy metal combined stabilizer, realize organic matter, phosphate fertilizer and nitrogen
Fertilizer, which is combined as stabilizer, is used for improvement and the ecological recovery of heavy-metal contaminated soil, can both be passivated the heavy metal in soil
It is stable, the effect of fertile soil can be reached again, the destruction to soil property is reduced as far as possible, be conducive to the recycling of soil.Meanwhile,
Rehabilitation cost can also be reduced, the recycling of solid waste is realized, the doulbe-sides' victory purpose of " treatment of wastes with processes of wastes against one another " is reached.The present invention
The second purpose be the application method that soil heavy metal combined stabilizer is provided, for heavy metal-polluted soil provided by the present invention
Compound stabilizer carries out test of many times, finds the rational dosage of soil heavy metal combined stabilizer, so as to ensure using most
Few usage amount reaches soil of the best processing by heavy metal pollution, realizes the reasonable utilization of natural resources.
To achieve these goals with some other purposes, the technical scheme that the present invention is provided is：
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：It is organic
Material 50-80%, phosphate fertilizer 16-40% and nitrogenous fertilizer 4-16%.
Including following components preferably, by mass percentage,：Organic substance 80%, phosphate fertilizer 16% and nitrogenous fertilizer
4%.
Preferably, the organic substance is any of natural decomposed cow dung or bacteria residue, and the phosphate fertilizer is peroxophosphoric acid
Calcium, the nitrogenous fertilizer is ammonium sulfate.
Preferably, the decomposed cow dung air-dries and 20 mesh sieves is crossed after crushing for the cow dung in the case of nature is become thoroughly decomposed, standby
With.
Preferably, it by remaining culture medium regulation water content after edible fungus culturing is 55% that the bacteria residue, which is, keeps equal
Even loose, compost fermentation is handled under the conditions of 70~80 DEG C, is mixed the compost after air-drying and was crushed 40 mesh sieves, standby.
A kind of application method of soil heavy metal combined stabilizer, it is characterised in that will be described soil heavy metal combined steady
Determine agent and processing 15 days is well mixed with the soil by heavy metal pollution in mass ratio 1: 5~8.
Preferably, by the soil heavy metal combined stabilizer and the soil in mass ratio 1: 7~8 by heavy metal pollution
Well mixed processing 15 days.
Preferably, soil moisture is kept after soil heavy metal combined stabilizer is added into the soil by heavy metal pollution
For 20~60%.
The beneficial effects of the invention are as follows：
(1) soil heavy metal combined stabilizer of the present invention be mainly characterized by rationally make use of decomposed cow dung, bacteria residue,
Calcium superphosphate and ammonium sulfate have given full play to the multiple of three class materials to the respective action principle of the heavy metals such as copper, lead, zinc, cadmium
Function.After bacteria residue+calcium superphosphate+ammonium sulfate compound stabilizer Passivation Treatment 15 days, zinc, copper, lead in soil, the leaching of cadmium
Go out toxic concentration drop to 302.90 from 464.00,332.50,363.50,1.61mg/L respectively, 43.86,0.42,0.75mg/
L, stabilization efficiency is respectively 31.78%, 85.23%, 99.88%, 52.94%.And effect is with the consumption, blunt of compound stabilizer
Change the increasing in reaction time and significantly increase, there is very big application value in vast heavy metal pollution area.
(2) heavy metal in soil can not only be passivated stabilization by soil heavy metal combined stabilizer of the present invention, and
And the material environment friendly used is stronger, raising soil organic matter content and cation exchange capacity (CEC) that can be by a relatively large margin reach
The purpose of fertile soil.
(3) heavy metal ion in polluted soil through soil heavy metal combined stabilizer treatment of the present invention can turn
Heavy metal-organic complex of relatively stable subcarbonate, hydroxide sediment, phosphate mineral and indissoluble is turned to,
So as to weaken the bioactivity of heavy metal.
(4) soil heavy metal combined stabilizer raw material sources of the present invention are easy to get extensively, and preparation and application is simple
Easy, rehabilitation cost is low, realizes the recycling to agricultural waste, reaches the doulbe-sides' victory purpose of " treatment of wastes with processes of wastes against one another ".
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
Embodiment 1
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Naturally
Decomposed cow dung 80%, calcium phosphate 16% and sulfuric acid 4%.
Embodiment 2
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Bacteria residue
80%, calcium phosphate 16% and sulfuric acid 4%.
Embodiment 3
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Naturally
Decomposed cow dung 70%, calcium phosphate 23% and sulfuric acid 8%.
Embodiment 4
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Bacteria residue
70%, calcium phosphate 22% and sulfuric acid 8%.
Embodiment 5
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Naturally
Decomposed cow dung 60%, calcium phosphate 28% and sulfuric acid 12%.
Embodiment 6
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Bacteria residue
60%, calcium phosphate 28% and sulfuric acid 12%.
Embodiment 7
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Naturally
Decomposed cow dung 50%, calcium phosphate 34% and sulfuric acid 16%.
Embodiment 8
A kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Bacteria residue
50%, calcium phosphate 34% and sulfuric acid 16%.
Embodiment 9
A kind of application method of soil heavy metal combined stabilizer is by the soil heavy metal combined stabilizer and by weight
The soil of metallic pollution in mass ratio 1: 5 is well mixed and keeps soil moisture to be 20%, handles 15 days.
Wherein, decomposed cow dung air-dries and 20 mesh sieves is crossed after crushing for the cow dung in the case of nature is become thoroughly decomposed, standby.Bacteria residue is
It is 55% by remaining culture medium regulation water content after edible fungus culturing, keeps uniform loose, the compost under the conditions of 70~80 DEG C
Fermentation process, mixes the compost after air-drying and crushed 40 mesh sieves, standby.
Embodiment 10
A kind of application method of soil heavy metal combined stabilizer is by the soil heavy metal combined stabilizer and by weight
The soil of metallic pollution in mass ratio 1: 8 is well mixed and keeps soil moisture to be 40%, handles 15 days.
Wherein, decomposed cow dung air-dries and 20 mesh sieves is crossed after crushing for the cow dung in the case of nature is become thoroughly decomposed, standby.Bacteria residue is
It is 55% by remaining culture medium regulation water content after edible fungus culturing, keeps uniform loose, the compost under the conditions of 70~80 DEG C
Fermentation process, mixes the compost after air-drying and crushed 40 mesh sieves, standby.
Embodiment 11
A kind of application method of soil heavy metal combined stabilizer is by the soil heavy metal combined stabilizer and by weight
The soil of metallic pollution in mass ratio 1: 6.5 is well mixed and keeps soil moisture to be 60%, handles 15 days.
Wherein, decomposed cow dung air-dries and 20 mesh sieves is crossed after crushing for the cow dung in the case of nature is become thoroughly decomposed, standby.Bacteria residue is
It is 55% by remaining culture medium regulation water content after edible fungus culturing, keeps uniform loose, the compost under the conditions of 70~80 DEG C
Fermentation process, mixes the compost after air-drying and crushed 40 mesh sieves, standby.
In laboratory conditions, the heavy-metal contaminated soil compound stabilizer of above-described embodiment 1 is answered with heavy metal-polluted soil
The application method for closing stabilizer is combined, and sets check experiment, and detection heavy-metal contaminated soil compound stabilizer is to by dirt
The soil of dye is handled：
Embodiment 12：
(1) preparation of heavy-metal contaminated soil compound stabilizer：1. the preparation of bacteria residue：From the bacteria residue wind after compost fermentation
It is standby that 40 mesh sieves are crossed in dry grinding；2. according to 80% bacteria residue, 16% calcium superphosphate, 4% ammonium sulfate carries out three kinds of components
Mixing, stirs, soil heavy metal combined stabilizer is made；
(2) mixed with soil：Compound stabilizer is equal with being mixed by heavy-metal contaminated soil according to mass ratio 1: 8
It is even, keep soil moisture content be 40%, while set one without passivation agent material experiment to control treatment；
(3) passivation reaction：Reacted through 15 days, the heavy metal in contaminated soil is stabilized, and its Leaching concentration is shown in Table
1.ZINC IN SOIL, copper, lead, cadmium, the stabilization efficiency of arsenic are respectively after the soil heavy metal combined stabilizer treatment of the data display of table 1
31.78%th, 85.23%, 99.88%, 52.94%
Toxicity leaching concentration mg/L before and after the passivation of the heavy metal in soil of table 1
Embodiment 13：
(1) preparation of heavy-metal contaminated soil Organic-inorganic composite stabilizer：1. the preparation of natural decomposed cow dung：From
Naturally cow dung after becoming thoroughly decomposed air-dries that to crush 40 mesh sieves standby；2. according to 80% decomposed cow dung, 16% calcium superphosphate, 4%
Ammonium sulfate three kinds of materials are mixed, stir, soil heavy metal combined stabilizer be made；
(2) mixed with soil：Compound stabilizer is equal with being mixed by heavy-metal contaminated soil according to mass ratio 1: 5
It is even, keep soil moisture content be 40%, while set one without passivation agent material experiment to control treatment；
(3) passivation reaction：Reacted through 15 days, the heavy metal in contaminated soil is stabilized, and its Leaching concentration is shown in Table
2.ZINC IN SOIL, copper, lead, cadmium, the stabilization efficiency of arsenic are respectively after soil heavy metal combined stabilizer treatment knowable to the data of table 2
78.97%th, 73.35%, 98.96%, 21.29%.
Toxicity leaching concentration mg/L before and after the passivation of the heavy metal in soil of table 2
In conjunction with the embodiments 12 and 13, organic matter combination phosphate fertilizer, nitrogenous fertilizer are can effectively to reduce heavy metal in soil to leach poison
Property concentration, dosage is more big more is conducive to the stabilization of heavy metal.
It is mainly copper, lead, zinc, cadmium by the heavy metal in the soil of heavy metal pollution.Foundation《Solid waste Leaching soaks
Go out method sulfonitric method》(HJ/T 299-2007) carries out leaching experiment, and degree is cut down according to the concentration of infusion solution heavy metal
To judge the stabilization efficiency of compound stabilizer heavy metal.Soil environment quality after reparation reaches country《Hazardous waste differentiates
Standard leaching characteristic identification》(GB5085.3-2007) requirement.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here embodiment.
Claims (5)
1. a kind of soil heavy metal combined stabilizer, it is characterised in that by mass percentage, including following components：Organic matter
Matter 60-80%, phosphate fertilizer 16-28% and nitrogenous fertilizer 4-12%, the organic substance are any in natural decomposed cow dung or bacteria residue
Kind, the phosphate fertilizer is calcium superphosphate, and the nitrogenous fertilizer is ammonium sulfate；The decomposed cow dung is that the cow dung in the case of nature is become thoroughly decomposed,
Air-dry and 20 mesh sieves are crossed after crushing, it is standby；It by remaining culture medium regulation water content after edible fungus culturing is 55% that the bacteria residue, which is,
Keep uniform loose, compost fermentation is handled under the conditions of 70~80 DEG C, is mixed the compost after air-drying and was crushed 40 mesh sieves, standby
With.
2. soil heavy metal combined stabilizer as claimed in claim 1, it is characterised in that by mass percentage, including with
Lower component：Organic substance 80%, phosphate fertilizer 16% and nitrogenous fertilizer 4%.
3. a kind of application method of soil heavy metal combined stabilizer as claimed in claim 1, it is characterised in that by the soil
Earth heavy metal compound stabilizer and the soil in mass ratio 1 by heavy metal pollution:5~8 well mixed processing 15 days.
4. the application method of soil heavy metal combined stabilizer as claimed in claim 3, by the soil heavy metal combined stabilization
Agent and the soil in mass ratio 1 by heavy metal pollution:7~8 well mixed processing 15 days.
5. the application method of soil heavy metal combined stabilizer as claimed in claim 3, it is characterised in that to by heavy metal pollution
Soil in add after soil heavy metal combined stabilizer keep soil moisture be 20~60%.
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| CN105295941A (en) * | 2015-11-23 | 2016-02-03 | 辛衷瑜 | Plant remains deactivator for passivating heavy metals in micropowder soil |
| CN105772496A (en) * | 2016-03-09 | 2016-07-20 | 浙江大学 | Farmland soil heavy metal blocking and controlling method |
| CN105820821B (en) * | 2016-05-18 | 2019-02-19 | 北京建筑材料科学研究总院有限公司 | A kind of lead zinc combined contamination soil immobilization medicament and preparation method thereof |
| CN108373391A (en) * | 2016-11-11 | 2018-08-07 | 贵州省烟草科学研究院 | It is a kind of to drop cadmium organic fertilizer and preparation method and application by the flue-cured tobacco of matrix of cow dung |
| CN106734123A (en) * | 2016-11-18 | 2017-05-31 | 东莞中科土壤科技开发有限公司 | A kind of composite conditioner repaired for heavy metal polluted soil of farmland and preparation method thereof |
| CN107936981A (en) * | 2017-11-15 | 2018-04-20 | 中国环境科学研究院 | Soil heavy metal combined passivator and preparation method thereof, application method and application |
| CN108976074A (en) * | 2018-06-30 | 2018-12-11 | 浙江瑞美生态建设股份有限公司 | A kind of heavy metal-polluted soil passivation renovation agent and its restorative procedure |
| CN112266069A (en) * | 2020-09-29 | 2021-01-26 | 西安工程大学 | Heavy metal ion compound stabilizer and preparation method thereof |
| CN114367532A (en) * | 2022-01-12 | 2022-04-19 | 云南农业大学 | Method for improving lead-zinc ore waste land and promoting plant reconstruction by adopting phosphogypsum and bacterial slag |
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