CN106967432A - A kind of agricultural land soil Compound Heavy Metals passivator and purposes - Google Patents
A kind of agricultural land soil Compound Heavy Metals passivator and purposes Download PDFInfo
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- CN106967432A CN106967432A CN201610020600.3A CN201610020600A CN106967432A CN 106967432 A CN106967432 A CN 106967432A CN 201610020600 A CN201610020600 A CN 201610020600A CN 106967432 A CN106967432 A CN 106967432A
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- soil
- heavy metals
- heavy metal
- compound heavy
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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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- 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
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
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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)
Abstract
The invention discloses a kind of soil Compound Heavy Metals in-situ passivation agent and purposes.Method is to add a certain proportion of passivator in Compound Heavy Metals soil to mix.The passivator is to utilize to be mixed according to different proportion containing multiple materials such as Ferromanganese Ore, zeolite, diatomite and flyash, Compound Heavy Metals validity in soil can effectively be reduced, including As, Cd, Pb, Cu, and substantially reduce absorption of the crops such as vegetables to each heavy metal, fundamentally prevent heavy metal from entering food chain, have the advantages that to take low, simple to operate short, cost, instant effect, easily promote, be a kind of economic, efficiently, safe soil Compound Heavy Metals passivator.
Description
Technical field
The invention belongs to heavy metal pollution of soil recovery technique field, and in particular to a kind of soil Compound Heavy Metals（Including arsenic, cadmium, lead, copper）Pollute fixative and purposes.The present invention can carry out Compound Heavy Metals to Compound Heavy Metals soil and fix, and the bio-available Zn concentration of each heavy metal, substantially reduces the absorption of crop heavy metal in reduction soil, fundamentally prevents heavy metal from entering food chain, ensures edible safety.
Background technology
Soil is one of natural resources for the survival of mankind, is also that the mankind obtain food and the material base of other regenerated resources.With developing rapidly for modern chemical industry agricultural, three industrial wastes and agricultural chemicals containing heavy metal, a large amount of apply of fertilizer cause the pollution of heavy metal in soil to turn into one of principal element of influence soil environment quality.Especially heavy-metal composite pollution is on the rise, and between element or chemicals is a very stubborn problem to the combined influence of biological effect in combined pollution.It is enriched in the top layer of soil, i.e. arable layer more external heavy metal, is the main place that crop absorbs nutrient.In order to fundamentally prevent heavy metal from entering food chain, it is necessary to heavy metal in soil pollution is repaired, the absorption of crop heavy metal is reduced.Heavy metal pollution and Environmental and ecological problems have seriously been related to the sustainable development of economy and the health of the mankind, receive the extensive concern of pedologist and environmentalists.Heavy metal pollution of soil recovery technique mainly includes physics, biological and chemical and repairs three kinds.Wherein chemical remediation have the advantages that simple to operate, cost is low, time-consuming short, efficiency high and be widely studied.
The content of the invention
Sorbing material of the present invention is mainly included containing Ferromanganese Ore, zeolite, flyash, diatomite etc., and this different materials is uniformly mixed according to certain proportioning, then is applied mixing in the soil of heavy metal pollution.The advantage of the present invention is to be repaired using the synergy of various materials for various heavy, including As, Cd, Pb, Cu etc..Material therefor is pollution-free heavy metals exceeding standard, does not result in secondary pollution.In addition, diatomite and zeolite can also can improve soil fertilizer and water-retaining property as soil conditioner.According to soil contamination grade Rational Application fixative, to reduce the absorption of crop heavy metal, human health is ensured.
Implement technical scheme as follows：
Several sorbing materials repaired suitable for soil Compound Heavy Metals, material is in terms of butt quality, and by soil quality percentage, the 0.5%-5% for the quality that is manured into soil respectively can be administered according to the specific pollution level of soil.
Suitable for the fixative of soil Compound Heavy Metals, counted using gross mass percentage as 100%, the fixation agent prescription of Compound Heavy Metals：
Containing Ferromanganese Ore（100-200 mesh）
30-60%；
Zeolite
（100-200 mesh）
10-40%；
Diatomite（100-200 mesh）
20-40%；
Flyash（100-200 mesh）
10-30%。
Follow these steps to apply：
Each sorbing material is well mixed by formula ratio, then is applied a certain amount of Compound Heavy Metals soil（Topsoil）It is middle to mix, add a certain amount of water（About 80% or so of field capacity）, place balance more than one week, sowing farming can be carried out after during which keeping ground moistening, balance.
The preferred scheme one of the present invention, containing Ferromanganese Ore, zeolite, diatomite and flyash, by mass percentage：
Counted using gross mass percentage as 100%：
Containing Ferromanganese Ore（100-200 mesh）
60%；
Zeolite
（100-200 mesh）
10%；
Diatomite（100-200 mesh）
20%；
Flyash（100-200 mesh）
10%。
The preferred scheme two of the present invention, containing Ferromanganese Ore, zeolite, diatomite and flyash, by mass percentage：
Counted using gross mass percentage as 100%：
Containing Ferromanganese Ore（100-200 mesh）
30%；
Zeolite
（100-200 mesh）
20%；
Diatomite（100-200 mesh）
20%；
Flyash（100-200 mesh）
30%。
The preferred scheme three of the present invention, containing Ferromanganese Ore, zeolite, diatomite and flyash, by mass percentage：
Counted using gross mass percentage as 100%：
Containing Ferromanganese Ore（100-200 mesh）
45%；
Zeolite
（100-200 mesh）
5%；
Diatomite（100-200 mesh）
40%；
Flyash（100-200 mesh）
10%。
Above-mentioned technical proposal proposed by the invention is that sorbing material can be applied in soil Compound Heavy Metals reparation.
Soil Compound Heavy Metals sorbing material prepared by the present invention is selected from the element material of generally existing in environment, including production waste material etc., nontoxic and cheap.According to market constant price, 1 ton of sorbing material of the invention is often prepared, cost RMB 492-532 members are about needed.According to the difference of soil Compound Heavy Metals degree, the fixation agent material of different proportion can be applied；It is different according to the ratio that fixed agent material is manured into soil, the soil of different area can be handled.Therefore when handling soil Compound Heavy Metals, it is economically viable to implement the present invention.
Soil Compound Heavy Metals fixative prepared by the present invention has good repairing effect.Calculated in the 0.5% of the ratio of being manured into soil and 5%, soil Compound Heavy Metals fixative per ton can repair about 200 tons and 20 tons of contaminated soils respectively.In theory, for the more serious soil of Compound Heavy Metals, the amount of the fixative of application is suitably increased；And for the lighter soil of Compound Heavy Metals, it is possible to reduce sowing amount.It should be noted that in soil Compound Heavy Metals, each heavy metal pollution degree is different, therefore, for the big heavy metal of pollution level, thus it is possible to vary the sorbing material ratio used in fixative, to reach best repair effect.If being no longer influenced by heavy metal pollution, and soil texture, acid-base property etc. by the contaminated soil repaired, big change does not occur, secondary pollution will not occur again for the soil.
The present invention technical principle be：
Using various materials common in life, according to existing result of study, filter out and each preferable different materials of single heavy metal fixed effect are mixed, so as to be repaired to Compound Heavy Metals soil.In the sorbing material of screening, each sorbing material is had nothing in common with each other for different heavy metal adsorptions and mechanism.
There is stronger adsorption capacity to arsenic containing Ferromanganese Ore, trivalent arsenic on the one hand can be oxidized to pentavalent arsenic containing the Mn oxide contained in Ferromanganese Ore, on the other hand, there is large surface area containing Ferromanganese Ore, surface site is more, there is very strong adsorption ability to arsenic.
There is abundant activated adoption site containing Ferromanganese Ore, it is preferable to the adsorption effect of pentavalent arsenic, and for Cd2+、Pb2+、Cu2+Etc. heavy metal ion, it may have stronger surface and Inter layer adsorption ability.
The three-dimensional structure of zeolite causes it to have very big space；Secondly, Al in tetrahedron3+Replace Si4+It can produce again local negatively charged；Na, Ca, K etc. positively charged exchangeable ion tends to take up cation Na and Ca etc. for being located in the space in structure, zeolite in passage and Si-Al backbones, and to contact power weaker, can be by other cation replacements without destroying character, therefore, for Cd2+、Pb2+、Cu2+These positively charged exchangeable ions can be substituted Deng heavy metal cation, so as to reach the effect of removing heavy metals.
Diatomite mainly contains Al2O3, Fe2O3, CaO, MgO, K2O, Na2O, P2O5 and organic matter.SiO2 generally accounts for more than 80%, reaches as high as 94%.The diatomaceous iron oxide content of high-quality is generally 1 ~ 1.5%, and alumina content is 3 ~ 6%.Diatomaceous mineral composition is mainly opal and its mutation, next to that clay mineral-hydromica, kaolinite and mineral chip.Due to the micropore with multistage a large amount of, ordered arrangement, therefore pore volume is big, aperture big, and specific surface area is big, and absorption property is strong, can effectively adsorb Cd2+、Pb2+、Cu2+Etc. heavy metal ion.Diatomite also contains substantial amounts of clay mineral, heavy metal ion, particularly to Cd2+、Pb2+、Cu2+Possess good exchangeability and Selective adsorption.
Flyash is alkaline matter, and particle diameter is small, porous and specific surface area is big, can most importantly improve soil pH, promotes the sediments such as the heavy metals such as Cd, Pb, Cu generation silicate, carbonate, hydroxide, so as to reduce the validity of heavy metal-polluted soil.
Experiment shows, above-mentioned fixed agent material is applied in the soil of Compound Heavy Metals, can effectively reduce the accumulation of crop overground part and root to each heavy metal, reduces heavy metal-polluted soil bio-available Zn concentration.And fixative applicating ratio is higher, the ability that reduction crop absorbs heavy metal is stronger.
The beneficial effects of the invention are as follows：
（1）The fixative material requested of the present invention is common, and preparation process is very simple, and raw material are mixed；
（2）The present invention is to Compound Heavy Metals in soil（As, Cd, Pb, Cu etc.）Fixed effect substantially, can significantly reduce the absorption of crop heavy metal, strengthen the safety of agricultural product；
（3）The present invention is applicable different degrees of heavy-metal contaminated soil, and the fixative of different proportion can be applied according to actual conditions, and fixative is with low cost, economically feasible.
Table
1
Table 1：It is fixative formula table of the present invention.
Brief description of the drawings
Fig. 1 is the bio-available Zn concentration change for implementing each heavy metal in soil after the not passivator of be the same as Example：Be the present invention under experimental conditions, embodiment 1, embodiment 2 and embodiment 3 are used for pakchoi potted plant experiment, the change block diagram of Compound Heavy Metals bio-available Zn concentration in potting soil.Soil used includes the pale brown soil in Daye and Xiangyang Sulfur fractions.Fig. 1 shows that embodiment 1-3 can reduce the validity of heavy metal in potting soil.
Fig. 2 implements pakchoi overground part content of beary metal after the not passivator of be the same as Example：Be the present invention under experimental conditions, embodiment 1, embodiment 2 and embodiment 3 be used for pakchoi potted plant experiment, to reduction pakchoi overground part absorb heavy metal-polluted soil effect block diagram.Soil used includes the pale brown soil in Daye and Xiangyang Sulfur fractions；Varieties of Brassica campestris is special Brassica rapa L.Fig. 2 shows that embodiment 1-3 can significantly reduce absorption of the pakchoi overground part to each heavy metal in soil.
Embodiment
Embodiment
1
：
It, containing Ferromanganese Ore, zeolite, diatomite and flyash, is based on 100% by gross mass percentage that material therefor, which is,：
Containing Ferromanganese Ore（100-200 mesh）
60%；
Zeolite
（100-200 mesh）
10%；
Diatomite（100-200 mesh）
20%；
Flyash（100-200 mesh）
10%。
Follow these steps to implement：
2% according to soil quality applies, i.e. 20g/kg.Aforementioned proportion material is weighed respectively, after being well mixed, admixes in a certain amount of soil and mixes together with base manure, be fitted into basin alms bowl, and regulation water content is 80% or so of field moisture（About the 20% of absolute water content）, covered with film, room temperature is placed, balance is sowed after 10 days.Culture is sampled for 5 weeks or so, determines accumulation of the pakchoi overground part to each heavy metal；Soil sampling, determines the bio-available Zn concentration of heavy metal in soil simultaneously.
The bio-available Zn concentration of each heavy metal is substantially reduced in two kinds of soil（Referring to Fig. 1）, compared with blank control, arsenic reduces 50% and 62% in pale brown soil and Sulfur fractions；Cadmium reduces 47% and 67%；Copper reduces 43% and 61%；Lead reduces 73% and 42%.
In potted plant experiment, apply after fixative, pakchoi overground part is significantly reduced to the accumulation of each heavy metal（Referring to Fig. 2）.Compared with blank control, overground part arsenic, cadmium, lead and copper reduce 72%, 55%, 60% and 37% respectively in pale brown soil.Overground part arsenic arsenic, cadmium, lead and copper reduce 74%, 58%, 67% and 49% respectively in Sulfur fractions.
Embodiment
2
：
It, containing Ferromanganese Ore, zeolite, diatomite and flyash, is based on 100% by gross mass percentage that material therefor, which is,：
Containing Ferromanganese Ore（100-200 mesh）
30%；
Zeolite
（100-200 mesh）
20%；
Diatomite（100-200 mesh）
20%；
Flyash（100-200 mesh）
30%。
Carried out according to the step of embodiment 1.As a result show, in potted plant experiment, apply pakchoi overground part after fixative significantly reduces to the accumulation of each heavy metal（Referring to Fig. 2）.Compared with blank control, overground part arsenic reduces 76% in pale brown soil；Cadmium reduces 60%；Lead reduces 68%；Copper reduces 63%.Overground part arsenic reduces 85% in Sulfur fractions；Cadmium reduces 59%；Lead reduces 79%；Copper reduces 73%.
The bio-available Zn concentration of each heavy metal is substantially reduced in two kinds of soil（Referring to Fig. 1）, compared with blank control, arsenic reduces 54% and 65% in pale brown soil and Sulfur fractions；Cadmium reduces 65% and 48%；Lead reduces 68% and 56%；Copper reduces 51% and 58%.
Embodiment
3
：
It, containing Ferromanganese Ore, zeolite, diatomite and flyash, is based on 100% by gross mass percentage that material therefor, which is,：
Containing Ferromanganese Ore（100-200 mesh）
45%；
Zeolite
（100-200 mesh）
5%；
Diatomite（100-200 mesh）
40%；
Flyash（100-200 mesh）
10%。
Carried out according to the step of embodiment 1.As a result show, in potted plant experiment, apply after fixative, pakchoi overground part is significantly reduced to the accumulation of each heavy metal（Referring to Fig. 2）.Compared with blank control, overground part arsenic reduces 81% and 87% respectively in pale brown soil and Sulfur fractions；Cadmium reduces 63% and 61% respectively；Lead reduces 79% and 81% respectively；Copper reduces 75% and 82% respectively.
The bio-available Zn concentration of each heavy metal also decreases in soil（Referring to Fig. 1）, compared with blank control, arsenic reduces 62% and 68% in pale brown soil and Sulfur fractions；Cadmium reduces 74% and 59%；Lead reduces 68% and 56%；Copper reduces 50% and 60%.
Fixed agent material used of the invention is pollution-free（Referring to table 2）, can be with safely use.
Table
2
Each sorbing material fundamental property
- represent not detect.
Claims (4)
1. a kind of soil Compound Heavy Metals in-situ passivation restoring material, it is characterised in that the repair materials are made up of 30-60% containing Ferromanganese Ore, zeolite 10-40%, diatomite 20-40% and flyash 10-30% by weight percentage；It is to take above-mentioned material ratio respectively, crushed 100-200 mesh, and stirred, dries and be made.
2. a kind of soil Compound Heavy Metals in-situ passivation material as claimed in claim 1, it is characterised in that the granularity after the material disintegrating is 100-200 mesh.
3. a kind of soil Compound Heavy Metals in-situ passivation restoring material as claimed in claim 1 or 2, it is characterised in that the repair materials are made up of 30-60% containing Ferromanganese Ore, zeolite 10-40%, diatomite 20-40%, and flyash 10-30% by weight percentage.
4. application of the Compound Heavy Metals soil remediation material in rehabilitating soil heavy metal pollution as any one of claim 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610020600.3A CN106967432A (en) | 2016-01-14 | 2016-01-14 | A kind of agricultural land soil Compound Heavy Metals passivator and purposes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610020600.3A CN106967432A (en) | 2016-01-14 | 2016-01-14 | A kind of agricultural land soil Compound Heavy Metals passivator and purposes |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110257078A (en) * | 2019-06-28 | 2019-09-20 | 中冶南方都市环保工程技术股份有限公司 | A kind of heavy metal curing agent and its preparation method and application based on iron and manganese oxides |
| CN110669524A (en) * | 2019-09-10 | 2020-01-10 | 铜仁市万山区植保植检站 | Cadmium-arsenic polluted soil remediation agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805617A (en) * | 2009-02-16 | 2010-08-18 | 中国科学院沈阳应用生态研究所 | Soil heavy metal passivant for facilities vegetable field and preparation method thereof |
| CN102174326A (en) * | 2011-03-11 | 2011-09-07 | 中国科学院亚热带农业生态研究所 | Heavy metal composite passivating agent used for paddy soil and preparation method thereof |
| KR101366069B1 (en) * | 2013-07-01 | 2014-03-07 | 주식회사 티에스이앤씨 | Composition for soil stabilization, improvement, hardening, and compost fermentation promotion of contaminated sediment, and method of manufacturing the same |
-
2016
- 2016-01-14 CN CN201610020600.3A patent/CN106967432A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805617A (en) * | 2009-02-16 | 2010-08-18 | 中国科学院沈阳应用生态研究所 | Soil heavy metal passivant for facilities vegetable field and preparation method thereof |
| CN102174326A (en) * | 2011-03-11 | 2011-09-07 | 中国科学院亚热带农业生态研究所 | Heavy metal composite passivating agent used for paddy soil and preparation method thereof |
| KR101366069B1 (en) * | 2013-07-01 | 2014-03-07 | 주식회사 티에스이앤씨 | Composition for soil stabilization, improvement, hardening, and compost fermentation promotion of contaminated sediment, and method of manufacturing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110257078A (en) * | 2019-06-28 | 2019-09-20 | 中冶南方都市环保工程技术股份有限公司 | A kind of heavy metal curing agent and its preparation method and application based on iron and manganese oxides |
| CN110669524A (en) * | 2019-09-10 | 2020-01-10 | 铜仁市万山区植保植检站 | Cadmium-arsenic polluted soil remediation agent |
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Application publication date: 20170721 |