CN113652234A - Modifier applicable to acid heavy metal contaminated soil and application thereof - Google Patents
Modifier applicable to acid heavy metal contaminated soil and application thereof Download PDFInfo
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- CN113652234A CN113652234A CN202111057076.4A CN202111057076A CN113652234A CN 113652234 A CN113652234 A CN 113652234A CN 202111057076 A CN202111057076 A CN 202111057076A CN 113652234 A CN113652234 A CN 113652234A
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- 239000002689 soil Substances 0.000 title claims abstract description 169
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 105
- 239000002253 acid Substances 0.000 title claims abstract description 72
- 239000003607 modifier Substances 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 141
- 239000004113 Sepiolite Substances 0.000 claims abstract description 38
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 38
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 38
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 37
- 239000010459 dolomite Substances 0.000 claims abstract description 35
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 35
- 230000002378 acidificating effect Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000010433 feldspar Substances 0.000 claims abstract description 6
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 6
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 29
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- 229910052588 hydroxylapatite Inorganic materials 0.000 description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 7
- 230000008635 plant growth Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- 230000006378 damage Effects 0.000 description 3
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 2
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
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- 238000007711 solidification Methods 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 208000019025 Hypokalemia Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOUFUOCPGSCPPN-UHFFFAOYSA-N [Pb].[P].[Cl] Chemical compound [Pb].[P].[Cl] BOUFUOCPGSCPPN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 239000002344 surface layer Substances 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- C05—FERTILISERS; MANUFACTURE THEREOF
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- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
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- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention provides a modifier suitable for acid heavy metal contaminated soil and application thereof. The modifier comprises, by weight, 15-25% of hydroxyapatite powder, 30-40% of sepiolite powder, 24-32% of montmorillonite powder, 15-25% of potash feldspar powder and 5-15% of dolomite powder. When the modifier is used in the construction process of an ecological restoration project of an extremely acidic mining area, excessive application of quicklime or hydrated lime and the like can be avoided, acid can be quickly eliminated, acid can be controlled, heavy metal toxicity can be reduced, the effect is quick, water and fertilizer can be preserved, crop resistance can be enhanced, meanwhile, the soil structure of the mining area can be continuously improved, medium and trace elements such as silicon, calcium, magnesium, phosphorus and the like can be slowly supplemented, the extremely acidic soil can be continuously improved for a long time, and secondary disasters can not be caused.
Description
Technical Field
The invention relates to the technical field of soil improvement, in particular to an improver applicable to acid heavy metal contaminated soil and application thereof.
Background
The non-ferrous metal mining is mainly open-pit mining, the area of the abandoned land of the Chinese mining industry is up to 200 hectares at the present stage, and the land occupied by the metal mine is 5 multiplied by 10 per year2km2The destruction speed of the land is continuously developed, so that the land loses economic utilization value. The activity of nonferrous metal mining is the most main source of heavy metal pollution in China, and the waste sulfur-containing rocks (mainly pyrite FeS)2) The acid waste water is easy to dissolve out heavy metals, and the same mining area usually contains a plurality of heavy metals, which causes environmental pollution together. Therefore, the extreme acidity of the soil of the metal mine dump and the toxicity of heavy metals seriously affect the growth and settlement of plants.
At present, the heavy metal contaminated soil of the extreme acid dumping field in China is improved by adopting in-situ matrix, and in the in-situ matrix improving process, the soil improvement agent needs to be applied to the extreme acid heavy metal contaminated soil to improve the physical and chemical properties of the soil, regulate acidity, control heavy metal pollution and improve fertility, so that the soil improvement agent is more suitable for plant growth.
The domestic technology for improving the acid soil is roughly divided into several types: (1) and (4) physical improvement. The method mainly comprises the steps of soil dressing, surface soil backfilling and the like, wherein before formal construction of a metal mining plant, the surface soil on the ground surface of the place needs to be stripped to reduce the probability of damaging a local soil seed bank, nutrient elements and a soil structure, and then the surface soil before mining needs to be backfilled to promote the accelerated recovery of local vegetation. (2) And (4) chemical improvement. Most metal mine wastelands are accompanied by relatively serious acidification problems, lime and bicarbonate are also beneficial to neutralizing the acid wastelands, and the heavy metal toxicity can be reduced by utilizing reactions such as complexation, precipitation, adsorption and the like between specific chemical substances and the heavy metal elements. (3) And (4) biological improvement. Biological improvement is also a technology for improving soil quality which is not ignored. For example, soil animals such as earthworms can be used, and the substrate can be improved by microorganisms such as enzymes and mycorrhiza.
Because the pH value of the extremely acidic soil in the metal mine dump can reach about 2.5, a few patents for repairing the heavy metal contaminated soil in the extremely acidic mining area are disclosed at present. Aiming at the extreme acidity of the polluted soil, the method mostly focuses on neutralizing the acid in the acid soil by adding alkaline neutralizers such as quicklime, slaked lime and limestone powder, and comprises the following steps:
chinese patent document (publication number: CN110860554A) discloses an improvement method for extremely acidified mine soil, which utilizes an improver and a microbial agent to change the microbial community structure of the soil, particularly reduces the relative abundance of iron-sulfur oxidation acid-producing microorganisms and inhibits metal sulfide oxidation acid-producing; the modifier can adsorb, chelate, complex and fix heavy metal ions, reduce the biological toxicity of the heavy metal ions and reduce the diffusion and leakage of the heavy metal ions to the surrounding soil or water. The improvement method has the advantages of low input cost, good acidification control and heavy metal stabilization effects, remarkable increase of the content of nutrient substances, no damage to the soil structure and easy implementation. According to the patent, a surface modifier (lime and farmyard manure) is covered on acidified mine soil, a microbial agent is applied to a soil lower layer, the microbial community structure of the soil is changed, particularly the relative abundance of iron-sulfur oxidation acid-producing microorganisms is reduced, and metal sulfide oxidation acid production is inhibited.
Chinese patent document (publication number: CN111423884A) discloses an acid soil conditioner and an application method and application thereof. The acid soil conditioner comprises biochar and hydrated lime, wherein the weight ratio of the biochar to the hydrated lime is (10-40) to (1.5-3); the biochar comprises pig manure pyrolytic carbon and/or rice straw carbon. The invention combines the biochar and the hydrated lime, can improve the soil problem caused by singly using the hydrated lime, avoids the defect that singly using the biochar has high cost and is not easy to be applied in a large scale, can improve the growth environment of crop roots, promotes the growth and absorption of roots, improves the nutrition and growth conditions, and increases the crop yield.
However, extreme acidification and heavy metal toxicity serve as two important influence factors for vegetation recovery and reconstruction of the metal mountain acidic dumping site, and the basis of vegetation recovery is that the soil ecological environment is improved. However, most soil conditioners have single effective component and high production cost in the currently adopted in-situ matrix improvement mode, and from the field effect, an acidified soil layer is easy to form soil hardening, and deep soil is prevented from curing and is not beneficial to the growth of the roots of the indigenous plants; on the other hand, in light, moderate and severe acidification areas, the soil structure is seriously damaged due to excessive spreading of quicklime and the like, the supply of nutrient elements such as nitrogen, phosphorus, potassium and the like is reduced, the plant growth is inhibited, and secondary disasters are easily caused by the modes.
Therefore, there is a need to provide a new amendment suitable for heavy metal contaminated soil in an extremely acidic waste dump, so as to avoid secondary disasters while effectively and continuously improving the extremely acidic heavy metal contaminated soil.
Disclosure of Invention
The invention mainly aims to provide a modifier suitable for acid heavy metal contaminated soil and application thereof, and aims to solve the problems that the modifier is insufficient in effective persistence and is easy to cause secondary disasters when used for modifying the acid heavy metal contaminated soil in the prior art.
In order to achieve the purpose, according to one aspect of the invention, the modifier suitable for the acid heavy metal contaminated soil is provided, and comprises 15-25% of hydroxyapatite powder, 30-40% of sepiolite powder, 24-32% of montmorillonite powder, 15-25% of potassium feldspar powder and 5-15% of dolomite powder by weight percentage.
Further, the modifier comprises 20-25 wt% of hydroxyapatite powder, 30-35 wt% of sepiolite powder, 24-28 wt% of montmorillonite powder, 15-20 wt% of potash feldspar powder and 5-8 wt% of dolomite powder.
Further, the weight ratio of the hydroxyapatite powder to the sepiolite powder is 0.720-0.833: 1.
Further, the weight ratio of the hydroxyapatite powder to the montmorillonite powder is 0.90-1.04: 1.
Further, the weight ratio of the hydroxyapatite powder to the potassium feldspar powder is 1.50-1.67: 1.
Further, the weight ratio of the hydroxyapatite powder to the dolomite powder is 3.0-5.0: 1.
Further, the modifier comprises 25 percent of hydroxyapatite powder, 30 percent of sepiolite powder, 24 percent of montmorillonite powder, 15 percent of potassium feldspar powder and 6 percent of dolomite powder in percentage by weight.
Further, the granularity of hydroxyapatite powder, sepiolite powder, montmorillonite powder, potassium feldspar powder and dolomite powder is 120-200 meshes respectively; preferably, the modifier is formed by mixing hydroxyapatite powder, sepiolite powder, montmorillonite powder, potassium feldspar powder and dolomite powder, or is formed by mixing and granulating hydroxyapatite powder, sepiolite powder, montmorillonite powder, potassium feldspar powder and dolomite powder, and the particle size of the granules is 2-4 mm.
According to another aspect of the invention, the improvement method of the acid heavy metal contaminated soil is also provided, and comprises the steps of applying the improver to the surface of the acid heavy metal contaminated soil and turning over the soil under the ground; preferably ploughed under the ground to a depth of 2-5 cm.
Further, when the pH value of the acid heavy metal contaminated soil is less than 5.5, the application amount of the modifying agent is 150-300 kg/mu; when the pH value of the acid heavy metal contaminated soil is 5.5-6.5, the application amount of the modifying agent is 100-150 kg/mu; preferably, organic fertilizer is also applied to the surface of the acidic heavy metal contaminated soil while the modifying agent is applied, wherein the application amount of the organic fertilizer is 3-10 kg/m2(ii) a Preferably, the organic fertilizer is selected from one or more of decomposed chicken manure and rice hull organic fertilizer, cow manure organic fertilizer and bottom mud organic fertilizer.
The invention provides a high-efficiency mineral modifier applicable to repairing of composite heavy metal contaminated soil in an extremely-acidified refuse dump in a metal mining area, which comprises hydroxyapatite powder, sepiolite powder, montmorillonite powder, potassium feldspar powder and dolomite powder, wherein the hydroxyapatite powder, the montmorillonite powder, the potassium feldspar powder and the dolomite powder are mixed by taking natural ores as raw materials. The modifier has the following remarkable effects: when the ecological restoration project is used in the construction process of the extremely acidic mining area ecological restoration project, excessive application of quicklime or hydrated lime and the like can be avoided, acid can be quickly eliminated and controlled, heavy metal toxicity is reduced, the effect is quick, water and fertilizer are retained, crop resistance is enhanced, meanwhile, the mining area soil structure can be continuously improved, medium and trace elements such as silicon, calcium, magnesium, phosphorus and the like are slowly and continuously supplemented, the extremely acidic soil is continuously improved for a long time, and secondary disasters cannot be caused.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a photograph showing germination of broadleaf grass on day 12 in group C according to example 1 of the present invention; and
FIG. 2 is a photograph showing the growth of broadleaf weeds on day 30 in group C according to example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Aiming at the environmental problems of extreme acidity, acid production, high heavy metal toxicity, serious impoverishment, too high proportion of acid-producing microorganisms and the like faced by the soil of a metal mine refuse dump, the in-situ soil matrix improvement in the field tends to select a multifunctional mineral substance high-efficiency modifying agent with less environmental damage and no secondary disaster, and can eliminate acid, preserve water and fertilizer, improve the soil gelatinization rate, repair compound heavy metal pollution, improve soil quality total nutrition, promote plant growth and reduce the construction cost.
In order to achieve the purpose, the invention provides a modifier suitable for acid heavy metal contaminated soil, which comprises 15-25 wt% of hydroxyapatite powder, 30-40 wt% of sepiolite powder, 24-32 wt% of montmorillonite powder, 15-25 wt% of potassium feldspar powder and 5-15 wt% of dolomite powder.
The components have the following multifunctional characteristics: 1) hydroxyapatite: promoting plant growth: sufficient phosphorus element is provided for plant growth, and the fertility is slowly released and lasting; raising the pH value of the soil, and reducing the toxicity of heavy metals: the heavy metal is adsorbed, precipitated and complexed with heavy metals such as Pb, Cu, Zn, Cd and the like in soil, the content of the effective state of the heavy metals, particularly the high-concentration heavy metal Pb, is obviously reduced, and the phosphorus-chlorine-lead ore mineral precipitate is formed through ion exchange. 2) Sepiolite, montmorillonite: the natural silicate clay minerals such as montmorillonite and sepiolite have the advantages of abundant resources, no environmental pollution and low price; secondly, the sepiolite and the alkaline material are both alkaline materials, and compared with montmorillonite, the sepiolite can obviously improve the pH value of the soil; passivating heavy metals, having larger specific surface area in nonmetallic minerals and strong adsorbability, and being capable of reducing the content of effective states of heavy metals; the sepiolite is a water-containing magnesium-rich silicate clay mineral with a layered chain structure, the montmorillonite is a layered mineral formed by water-containing aluminosilicate, has high water-absorbing expansion capacity, strong adsorption capacity and cation exchange performance, can effectively replace heavy metal ions, has good water-retaining effect, can improve the physical structure of soil, improves the permeability of the soil and improves the fertilizer supply capacity of the soil. 3) Potassium feldspar powder: the raw material can be utilized to provide silicon and potassium elements for acid soil well, make up for the defect of potassium deficiency of the acid soil, and provide sufficient silicon and potassium elements for plant growth. 4) Dolomite powder: the carbonate mineral, the main component of which is calcium carbonate, is alkalescent, improves the pH value of soil, improves the physical properties of the soil and reduces soil hardening.
More importantly, the modifier simultaneously contains the ore powder, and each component can play a respective effect and can be matched with other components, so that a synergistic effect is achieved, and the modifier has a remarkable improvement effect on the acid heavy metal polluted soil.
In conclusion, the modifier provided by the invention has the following remarkable effects: when the ecological restoration project is used in the construction process of the extremely acidic mining area ecological restoration project, excessive application of quicklime or hydrated lime and the like can be avoided, acid can be quickly eliminated and controlled, heavy metal toxicity is reduced, the effect is quick, water and fertilizer are retained, crop resistance is enhanced, meanwhile, the mining area soil structure can be continuously improved, medium and trace elements such as silicon, calcium, magnesium, phosphorus and the like are slowly and continuously supplemented, the extremely acidic soil is continuously improved for a long time, and secondary disasters cannot be caused. Particularly, the conditioner is matched with organic farmyard manure for use, so that the plant recovery effect is better, acid can be eliminated, heavy metal in soil can be reduced, energy can be saved, carbon can be reduced, and the problem of soil productivity reduction can be solved.
The conditioner disclosed by the invention is simple in formula preparation, wide and cheap in raw materials, green and environment-friendly, and suitable for large-scale popularization and use in acid soil, especially in the in-situ matrix improvement of extremely acid waste dump soil, especially in the majority of metal mining areas in the south, such as heavy metal contaminated soil of extremely acidified waste dumps in pyrite, lead-zinc mine and the like, or in other types of acidified degraded soil improvement and vegetation reconstruction in mining areas.
For the purpose of further improving the soil improvement effect, in a preferred embodiment, the improver comprises 20-25% of hydroxyapatite powder, 30-35% of sepiolite powder, 24-28% of montmorillonite powder, 15-20% of potassium feldspar powder and 5-8% of dolomite powder by weight percentage.
As mentioned above, in addition to the properties of the above mineral powder, it is more important that the mineral powder is matched with other components to exert a better synergistic effect on the soil polluted by acidic, especially extremely acidic heavy metals. For this purpose, in a preferred embodiment, the weight ratio of the hydroxyapatite powder to the sepiolite powder is 0.720 to 0.833: 1. More preferably, the weight ratio of the hydroxyapatite powder to the montmorillonite powder is 0.90-1.04: 1. More preferably, the weight ratio of the hydroxyapatite powder to the potassium feldspar powder is 1.50-1.67: 1. More preferably, the weight ratio of the hydroxyapatite powder to the dolomite powder is 3.0-5.0: 1.
In one embodiment of the invention, the modifier comprises, by weight, 25% of hydroxyapatite powder, 30% of sepiolite powder, 24% of montmorillonite powder, 15% of potassium feldspar powder and 6% of dolomite powder. The content of each component in the improver is controlled to be above numerical value, so that the improver has higher soil improvement effect and has better and obvious effects on the aspects of acid elimination, soil heavy metal reduction and long-term continuous soil improvement.
The granularity of the hydroxyapatite powder, the sepiolite powder, the montmorillonite powder, the potash feldspar powder and the dolomite powder is preferably 120-200 respectively. The material can be prepared by stirring and mixing the components uniformly according to a certain mass percentage; the granules can also be prepared by extrusion granulation, the mixing equipment is a stirrer, the granulating equipment is a pair-roller granulator, and the particle size of the prepared granules is 2-4 mm.
In a word, the selected components of the modifier are hydroxyapatite, sepiolite, montmorillonite, potassium feldspar powder and dolomite powder, natural ores are used as raw materials, the source is wide, the cost is low, the field preparation is simple, the energy is saved, and the emission is reduced; the modifier is applied together with organic fertilizers formed by decomposing chicken manure, cow manure, sheep manure and the like, has the characteristics of novelty, greenness, environmental protection and high efficiency, can realize the double promotion effects of improving the soil fertility and reducing the toxicity of compound heavy metals, and effectively solves two problems (heavy metal toxicity and extreme acidity) of ecological restoration of the extremely acidic soil in the metal mining area; the method has the advantages of avoiding using lime and the like in site construction, not causing secondary disasters, having multiple functions, quickly eliminating acid, adjusting acid and alkali, reducing the content of effective states of heavy metals, improving the permeability of soil, supplementing medium and trace elements such as silicon, calcium, magnesium, phosphorus and the like, preserving water and fertilizer, continuously improving extremely acidic soil for a long time, and quickly promoting plant growth.
According to another aspect of the invention, the invention also provides a method for improving the soil polluted by the acid heavy metal, which is to apply the modifying agent on the surface of the soil polluted by the acid heavy metal and turn over the soil under the ground; preferably ploughed under the ground to a depth of 2-5 cm. The modifier can quickly eliminate and control acid, reduce heavy metal toxicity, quickly take effect, preserve water and fertilizer, enhance crop resistance, continuously improve the soil structure of a mining area, slowly release and supplement medium and trace elements such as silicon, calcium, magnesium, phosphorus and the like, continuously improve extremely acidic soil for a long time and do not cause secondary disasters. And in order to exert better effect, plowing to the depth of 5cm under the ground is the best. The specific ploughing mode can be simple ploughing by hoes, picks, shovels and the like, and the specific spreading mode can be bottom application, arbor and shrub hole application, strip ditch application and the like.
In a preferred embodiment, when the pH value of the acidic heavy metal contaminated soil is less than 5.5, the application amount of the modifying agent is 150-300 kg/mu when the matrix of the compound heavy metal contaminated soil in a waste dump is modified, wherein the matrix comprises very strong acid (the pH of the soil is less than 4.5) or strong acid (the pH of the soil is between 4.5 and 5.5); when the pH value of the acidic heavy metal contaminated soil is 5.5-6.5, for example, when the heavy metal soil matrix of other acidic mining area types such as general acidic (5.5-6.5) abandoned land is improved, the application amount of the modifying agent is 100-150 kg/mu.
Preferably, organic fertilizer is also applied to the surface of the acidic heavy metal contaminated soil while the modifying agent is applied, wherein the application amount of the organic fertilizer is 3-10 kg/m2. The conditioner is matched with organic farmyard manure for use, so that the plant recovery effect is better, acid can be eliminated, heavy metal in soil can be reduced, energy can be saved, carbon can be reduced, and the problem of soil productivity reduction can be solved. Preferably, the organic fertilizer is selected from one or more of decomposed chicken manure and rice hull organic fertilizer, cow manure organic fertilizer and bottom mud organic fertilizer.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
Repairing effect of different treatment methods on extremely acidic heavy metal combined polluted soil in metal mining area
(1) Test materials: the soil to be tested is collected from extremely acidic polluted soil in a mine dump, 3.5kg of the soil to be tested is weighed by a 5mm sieve in each basin, and the pH value of the soil in the mine area to be tested is 2.5-3.5.
The formula of the high-efficiency mineral modifier comprises: 25% of hydroxyapatite, 30% of sepiolite powder, 24% of montmorillonite powder, 15% of potassium feldspar powder and 6% of dolomite powder; the particle size of the stone powder is 120-200 meshes, and 200 kilograms of the stone powder is applied to each mu, about 330g/m2；
Completely decomposed chicken manure and rice hull organic fertilizer (pure chicken)2 portions of manure) and the using amount is 5kg/m2。
(2) Selecting the air-dried broad-leaved grass seeds after being soaked in distilled water for 1 hour. Sowing 500 grass seeds in each pot, about 0.75 g; the pot was set up in 3 groups, each of which was repeated 3 times.
Group A: adding the high-efficiency mineral modifier into soil 5cm deep from the surface soil of the flowerpot, and uniformly stirring, wherein the addition amount of each pot is 150g/kg, and the number is AM 1; group B: the flowerpot soil and the high-efficiency mineral modifier are completely and uniformly mixed, and the addition amount is 300 g/kg; group C: the high-efficiency mineral modifier is uniformly mixed with soil with the surface layer being 5CM, 50g/kg of chicken manure and rice hull organic fertilizer is added, and the mixture is uniformly stirred, and the number of the mixture is AM + CM. Set 1 group control CK. 1000mL of water was added after sowing of the grass seeds. The addition amounts of the modifying agents and the chicken manure and rice hull organic fertilizer of different groups are shown in a table 1:
TABLE 1
(3) The repairing effect is as follows:
the grass biomass of the broadleaf weeds in the groups after growing for 90 days is shown in table 2, and the grass biomass of the C group which is obtained by combining the high-efficiency mineral modifier with the organic fertilizer of the chicken manure and the rice hulls after growing for 90 days is respectively 9.3 times and 5.2 times of that of the A, B group which is singly used.
The physicochemical properties of the soil after 90 days of improvement of the heavy metal contaminated soil of the extreme acid dump by the broadleaf weeds are shown in Table 3. The original soil in the mine is extremely acidified, has a pH of only 2.3, and is quite barren. Compared with a control CK, the group C using the high-efficiency mineral modifier in combination with the chicken manure and rice hull organic fertilizer has the advantages that the pH of soil is increased by 4.8 units, organic matters reach 15.5g/kg, and the contents of quick-acting nitrogen and quick-acting potassium are remarkably increased to 109mg/kg and 195mg/kg respectively.
After the wide-leaf weeds grow for 90 days, the total state content, the effective state content and the solidification rate of heavy metals in the soil are subjected to comparative treatment, so that the effective state content of four heavy metals including Pb, Cu, Zn and Cd in the group C used by the high-efficiency mineral modifier and the organic fertilizer of chicken manure and rice hulls is obviously reduced, and the solidification rates of Pb, Cu, Zn and Cd are respectively 83.91%, 83.59%, 83.37% and 78.34% compared with those of the group A and the group B.
The results of the total and effective heavy metal content in the soil after 90 days of improvement of the heavy metal contaminated soil in the extreme acid dump by the broadleaf weeds are shown in table 4. After 90 days of remediation of the extremely acidic heavy metal contaminated soil in the mining area, the broadleaf weeds grow rapidly, the extremely acidic soil is obviously improved, the toxicity of the heavy metal is obviously reduced, the fertility level of the soil is obviously increased, and the soil environment required by vegetation recovery is achieved.
TABLE 4
Fig. 1 and fig. 2 show the germination condition and the growth condition of broadleaf grass on day 12 and day 30 of the group C, respectively, and it can be seen that the group of broadleaf grass grows fast, and leaves are dense, strong and energetic.
Example 2
The difference from group C in example 1 is only the formula of the modifier, and the formula of the high-efficiency mineral modifier is as follows: 23.25 percent of hydroxyapatite, 30 percent of sepiolite powder, 24 percent of montmorillonite powder, 15 percent of potassium feldspar powder and 7.75 percent of dolomite powder; the application amount is 200 kg per mu and is about 330g/m2. Record as D group.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 3
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 24% of hydroxyapatite, 30% of sepiolite powder, 24% of montmorillonite powder, 16% of potassium feldspar powder and 6% of dolomite powder; the application amount is 200 kg per mu and is about 330g/m2. And recording as the E group.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 4
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 23.2 percent of hydroxyapatite, 30 percent of sepiolite powder, 25.8 percent of montmorillonite powder, 15 percent of potassium feldspar powder and 6 percent of dolomite powder; the application amount is 200 kg per mu and is about 330g/m2. And is recorded as F group.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 5
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 23% of hydroxyapatite, 32% of sepiolite powder, 24% of montmorillonite powder, 15% of potassium feldspar powder and 6% of dolomite powder; the application amount is 200 kg per mu and is about 330g/m2. And recording as a group G.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 6
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 20% of hydroxyapatite powder, 35% of sepiolite powder, 24% of montmorillonite powder, 15% of potassium feldspar powder and 6% of dolomite powder. Record as group H.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 7
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 20% of hydroxyapatite powder, 30% of sepiolite powder, 28% of montmorillonite powder, 17% of potassium feldspar powder and 5% of dolomite powder. Record as group I:
the repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 8
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 20% of hydroxyapatite powder, 30% of sepiolite powder, 24% of montmorillonite powder, 18% of potassium feldspar powder and 8% of dolomite powder. Record as group J.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 9
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 20% of hydroxyapatite powder, 30% of sepiolite powder, 24% of montmorillonite powder, 20% of potassium feldspar powder and 6% of dolomite powder. And recording as K groups.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 10
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 15% of hydroxyapatite powder, 40% of sepiolite powder, 24% of montmorillonite powder, 15% of potassium feldspar powder and 6% of dolomite powder. And recording as L group.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
Example 11
The only difference from group C in example 1 is the modifier formulation: the formula of the high-efficiency mineral modifier comprises: 15% of hydroxyapatite powder, 30% of sepiolite powder, 32% of montmorillonite powder, 15% of potassium feldspar powder and 8% of dolomite powder. Is recorded as M groups.
The repairing effect is as follows: the herbaceous biomass is shown in table 2 after the broadleaf weeds grow for 90 days, the soil physicochemical properties after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 3, and the total and effective content results of the heavy metals in the soil after the broadleaf weeds improve the heavy metal contaminated soil of the extreme acid waste dump for 90 days are shown in table 4.
TABLE 2
| Numbering | Biomass dry weight (g/pot) |
| CK | 0 |
| Group A | 66.68 |
| Group B | 118.80 |
| Group C | 623.27 |
| Group D | 608.59 |
| Group E | 568.59 |
| Group F | 603.52 |
| Group G | 505.18 |
| Group H | 477.12 |
| Group I | 485.56 |
| J group | 503.49 |
| Group K | 492.72 |
| Group L | 458.82 |
| M groups | 445.96 |
TABLE 3
TABLE 4
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The modifier suitable for the acid heavy metal contaminated soil is characterized by comprising 15-25 wt% of hydroxyapatite powder, 30-40 wt% of sepiolite powder, 24-32 wt% of montmorillonite powder, 15-25 wt% of potash feldspar powder and 5-15 wt% of dolomite powder.
2. The improver according to claim 1, wherein the improver comprises 20 to 25% by weight of the hydroxyapatite powder, 30 to 35% by weight of the sepiolite powder, 24 to 28% by weight of the montmorillonite powder, 15 to 20% by weight of the potassium feldspar powder, and 5 to 8% by weight of the dolomite powder.
3. Improver according to claim 1 or 2, characterized in that the weight ratio of the hydroxyapatite powder to the sepiolite powder is 0.720 to 0.833: 1.
4. The improver according to claim 3, wherein the weight ratio of the hydroxyapatite powder to the montmorillonite powder is 0.90-1.04: 1.
5. Improver according to claim 4, wherein the weight ratio of the hydroxyapatite powder to the potassium feldspar powder is 1.50 to 1.67: 1.
6. Improver according to claim 5, wherein the weight ratio of the hydroxyapatite powder to the dolomite powder is 3.0 to 5.0: 1.
7. Improver according to claim 1, characterized in that it comprises, in percentages by weight, 25% of said hydroxyapatite powder, 30% of said sepiolite powder, 24% of said montmorillonite powder, 15% of said potash feldspar powder and 6% of said dolomite powder.
8. The improver according to claim 1, wherein the hydroxyapatite powder, the sepiolite powder, the montmorillonite powder, the potash feldspar powder and the dolomite powder have a particle size of 120 to 200 mesh; preferably, the modifier is formed by mixing the hydroxyapatite powder, the sepiolite powder, the montmorillonite powder, the potassium feldspar powder and the dolomite powder, or is formed by mixing and granulating the hydroxyapatite powder, the sepiolite powder, the montmorillonite powder, the potassium feldspar powder and the dolomite powder, and the particle size of the granules is 2-4 mm.
9. A method for improving acidic heavy metal contaminated soil, which comprises applying the improver according to any one of claims 1 to 8 to the surface of the acidic heavy metal contaminated soil and plowing the soil under the ground; preferably ploughed under the ground to a depth of 2-5 cm.
10. The improved method of claim 9,
when the pH value of the acid heavy metal contaminated soil is less than 5.5, the application amount of the modifying agent is 150-300 kg/mu;
when the pH value of the acid heavy metal contaminated soil is 5.5-6.5, the application amount of the modifying agent is 100-150 kg/mu;
preferably, organic fertilizer is also spread on the surface of the acidic heavy metal contaminated soil while the modifying agent is spread, wherein the spreading amount is 3-10 kg/m2(ii) a Preferably, the organic fertilizer is selected from rotten cooked chickenOne or more of organic fertilizer of manure and rice hull, organic fertilizer of cow manure and organic fertilizer of bottom mud.
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