CN107674682A - A kind of copper mine soil-repairing agent and preparation method thereof - Google Patents

A kind of copper mine soil-repairing agent and preparation method thereof Download PDF

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Publication number
CN107674682A
CN107674682A CN201710822668.8A CN201710822668A CN107674682A CN 107674682 A CN107674682 A CN 107674682A CN 201710822668 A CN201710822668 A CN 201710822668A CN 107674682 A CN107674682 A CN 107674682A
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CN
China
Prior art keywords
soil
copper mine
repairing agent
gained
copper
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Pending
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CN201710822668.8A
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Chinese (zh)
Inventor
胡明海
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Tongling Industry And Trade Co Ltd Yongxing Industry And Trade Co Ltd
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Tongling Industry And Trade Co Ltd Yongxing Industry And Trade Co Ltd
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Priority to CN201710822668.8A priority Critical patent/CN107674682A/en
Publication of CN107674682A publication Critical patent/CN107674682A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of copper mine soil-repairing agent and preparation method thereof, it is made up of raw materials such as alkali ore, PAMC, peat, ardealite, flyash, diopside, iron chloride, raw material sources of the present invention are extensive, renovation technique flow is simple, it can combine with general farming activity, soil texture and plantation function are not destroyed, do not bring heavy metal element into, non-secondary pollution, repairing effect are lasting, reclaimed for Copper Mine Abandoned Place to chemurgy, recover fertility and create condition, be suitable for being widely applied.

Description

A kind of copper mine soil-repairing agent and preparation method thereof
Technical field
The present invention relates to technical field of land improvement, more particularly to a kind of copper mine soil-repairing agent and preparation method thereof.
Background technology
In recent years, the land area discarded due to copper mining increases year by year, and the Abandoned Land of Mine of large area not only subtracts Available land resource is lacked, while many negative effects is also generated to region environment.Copper mine exploitation causes dirt The soil of dye mainly includes field of opencast mining, refuse dump, tailingspile, subsidence area and periphery and is polluted by copper metal and lose economy The soil of value.This kind of contaminated soil typically has following feature:Physical arrangement is bad, and water holding fertilizer-preserving ability is poor; It is extremely barren, organic matter and N, P, K nutrient deficiency;The kish of high concentration;Extreme ph values;Top layer is unstable and top layer Difference variation is big.Mine land is polluted because of copper metal very high concentrations, easily gives periphery soil by approach such as soil erosion and anemochory Carry out serious pollution with agrarian zone, and its environment influences have the characteristics that generality, seriousness, persistence and regionality.How Heavy Metal in Soil of Mining is effectively administered, it is that current copper mine ecological environmental protection is outstanding to recover its normal Ecological Functions It is the urgent task that Soil Pollution Control is faced.
At present, mainly there are in-situ immobilization and showering to the restorative procedure of copper polluted soil both at home and abroad.Showering is Contaminated soil is transferred in neighbouring place or reactor from contaminated area, using electrochemical process, elution method, chemical oxygen Change method etc. is administered contaminated soil.This recovery technique is related to bulk excavation and muck haulage, processing cost is high, destroys Soil texture, be not suitable for the improvement of pollution in wide area soil.In-situ immobilization is to pollute live treatment in situ pollutant.Base in situ Matter improving technology is to add one or more active materials to contaminated soil, and copper is improved in soil by changing soil physico-chemical property Middle adsorption capacity, or directly act on forming the small complex compound of solubility or precipitation with copper metal, so as to reduce copper in soil Mobility and biological effectiveness, in favor of plant growth and colonization, reach the purpose of restoration of the ecosystem contaminated soil.The technical costs It is low, quick, do not destroy soil texture, be easy to implement, suiting large area to popularize, be especially suitable for copper mine heavy metal pollution The improvement of soil.
In numerous in-situ remediation materials, nano zero valence iron removes multiple pollutant because being used to strong reducing property, High efficiency is shown in Treatment of Copper soil.Nano zero valence iron not only has the property of Zero-valent Iron, the advantage is that than common Zero-valent Iron has bigger specific surface area, higher reactivity and more preferable absorption property.However, nano zero-valence iron particle Surface energy it is higher, its particle is prone to reunite for more stable presence, formed submicron order either it is micron-sized Larger particles, cause Zero-valent Iron specific surface area and redox potential increase, so as to reduce contaminant removal efficiency, lose its work For the advantage of nano material.Which limits application of the zeroth order Nanoscale Iron in terms of pollution amelioration.
The content of the invention
The defects of the object of the invention is exactly to make up prior art, there is provided a kind of copper mine soil-repairing agent and its preparation Method.
The present invention is achieved by the following technical solutions:
A kind of copper mine soil-repairing agent, is prepared by the following method:
(1)Alkali ore be crushed into 120-150 mesh sieves, then with PAMC 4-6 in mass ratio:Heated after 1 mixing Stirred to 50-60 DEG C, it is standby to obtain cladding alkali miberal powder end;
(2)Diopside is sent into ground 200-220 mesh sieves in ball mill, by quality such as the diopside powder under sieving and calcium carbonate After mixing plus water is stirred, and well mixed mixture is dried at 100-110 DEG C, then is sent in roaster, with 20-25 DEG C/minute is warming up to 1000-1100 DEG C and is kept for more than 1 hour, and roasting product is naturally cooled into room temperature afterwards, It is fully levigate rear standby;
(3)By step 2 gained powders calcined and iron chloride in mass ratio 6:(4-5)30% ethanol of 3-4 times of quality of input is molten jointly In liquid, 10-12 hours are stirred continuously, then add into mixed liquor the 0.8mol/L of 2-2.5 times of volume sodium borohydride solution, Continue to stir 30-40 minutes under nitrogen protection, after the completion of be filtered by vacuum, gained solid is first washed with water 2-3 times, then with anhydrous Ethanol be washed once, and clean solid is placed under 75-85 DEG C of environment and dries 12-16 hours, obtain being modified after levigate diopside- Nano zero valence iron composite powder is standby;
(4)By peat, ardealite, flyash (2-3) in mass ratio:1:1.5 mixing after air-dry, remove mixture in stone, Levigate 80-100 mesh sieves excessively are standby after the debris such as grass cuttings;
(5)By cladding alkali miberal powder end, step 3 gained composite powder and step 4 gained compound obtained by step 1 in mass ratio (3-4):(2-4):(10-12)It is granulated in mixing input comminutor, gained particle is renovation agent of the present invention.
The alkali ore is any one in dolomite, aegirine-augite, calcite, potassium feldspar.
Diopside vibrates 18-24 hours at room temperature using being preceding immersed in 1mol/L salpeter solutions in the step 2, To remove soluble impurity, afterwards with being used after clear water cleaning, drying.
Stir speed (S.S.) is controlled at 180-220 revs/min under nitrogen protection in the step 3.
The application method of the copper mine soil-repairing agent, the uniform broadcasting of copper mine soil-repairing agent is polluted in copper mine Soil surface, ploughing soil is carried out, the wherein amount of application of renovation agent is the 4-8% of soil quality, and repair time is 30-60 days.
It is an advantage of the invention that:
The present invention be directed to copper mine contaminated soil, by peat, ardealite etc. be rich in a variety of organo-functional group materials use come The bioavailability of the heavy metal contaminants such as copper is reduced, the diopside after high temperature modified has oh group to enter molecule knot In structure, particle is in irregular, disperses relatively to open, while particle surface has many apertures and striped, improves specific surface area, increase Adsorption strength, adds decentralization after being combined with nano zero valence iron, reduces the reunion of nano zero valence iron, make its specific surface area Increase, thus number of active sites increase, the presence of diopside-nano zero valence iron composite particles allow its to copper ion simultaneously Adsorbed and precipitate reduction, iron oxygen and hydroxide therein are acted on the hydroxyl group contained in soil by surface complexation By copper absorption in material surface, the normal reduction potential of copper is higher than iron, thus Zero-valent Iron can lose electronics as electron source, Copper ion is reduced to zerovalent copper, the copper precipitation for being reduced to zeroth order is attached to the surface of inorganic agent, realizes copper in cupric soil The efficient absorption of ion, reclaimed to chemurgy for Copper Mine Abandoned Place, recover fertility and create condition, raw material of the present invention Wide material sources, renovation technique flow is simple, can combine with general farming activity, does not destroy soil texture and plantation work( , heavy metal element can not be brought into, non-secondary pollution, repairing effect are lasting, are suitable for being widely applied.
Embodiment
A kind of copper mine soil-repairing agent, is prepared by the following method:
(1)Dolomite be crushed into 120 mesh sieves, then with PAMC in mass ratio 4:50 DEG C are heated to after 1 mixing Stir, it is standby to obtain cladding alkali miberal powder end;
(2)Diopside is immersed in 1mol/L salpeter solutions, vibrated 18 hours at room temperature, to remove soluble impurity, it Ground 200 mesh sieve in ball mill is sent into after using clear water cleaning, drying afterwards, by quality such as the diopside powder under sieving and calcium carbonate After mixing plus water is stirred, and well mixed mixture is dried at 100 DEG C, then is sent in roaster, with 20 DEG C/ Divide and be warming up to 1000 DEG C and kept for more than 1 hour, roasting product is naturally cooled into room temperature afterwards, abundant levigate standby With;
(3)By step 2 gained powders calcined and iron chloride in mass ratio 6:5 put into 30% ethanol solution of 3 times of quality jointly, Be stirred continuously 10 hours, then into mixed liquor add 2 times of volumes 0.8mol/L sodium borohydride solution, under nitrogen protection with 200 revs/min continue stirring 30 minutes, after the completion of be filtered by vacuum, gained solid is first washed with water 2 times, then is washed with absolute ethyl alcohol Wash once, clean solid is placed under 75 DEG C of environment and dried 12 hours, obtain being modified diopside nano zero valence iron after levigate and answer It is standby to close powder;
(4)By peat, ardealite, flyash in mass ratio 3:1:Air-dried after 1.5 mixing, stone, grass cuttings in removal mixture It is standby Deng the levigate mesh sieve of mistake 80 after debris;
(5)By cladding alkali miberal powder end, step 3 gained composite powder and step 4 gained compound in mass ratio 4 obtained by step 1: 3:It is granulated in 12 mixing input comminutors, gained particle is renovation agent of the present invention.

Claims (5)

1. a kind of copper mine soil-repairing agent, it is characterised in that be prepared by the following method:
(1)Alkali ore be crushed into 120-150 mesh sieves, then with PAMC 4-6 in mass ratio:Heated after 1 mixing Stirred to 50-60 DEG C, it is standby to obtain cladding alkali miberal powder end;
(2)Diopside is sent into ground 200-220 mesh sieves in ball mill, by quality such as the diopside powder under sieving and calcium carbonate After mixing plus water is stirred, and well mixed mixture is dried at 100-110 DEG C, then is sent in roaster, with 20-25 DEG C/minute is warming up to 1000-1100 DEG C and is kept for more than 1 hour, and roasting product is naturally cooled into room temperature afterwards, It is fully levigate rear standby;
(3)By step 2 gained powders calcined and iron chloride in mass ratio 6:(4-5)30% ethanol of 3-4 times of quality of input is molten jointly In liquid, 10-12 hours are stirred continuously, then add into mixed liquor the 0.8mol/L of 2-2.5 times of volume sodium borohydride solution, Continue to stir 30-40 minutes under nitrogen protection, after the completion of be filtered by vacuum, gained solid is first washed with water 2-3 times, then with anhydrous Ethanol be washed once, and clean solid is placed under 75-85 DEG C of environment and dries 12-16 hours, obtain being modified after levigate diopside- Nano zero valence iron composite powder is standby;
(4)By peat, ardealite, flyash (2-3) in mass ratio:1:1.5 mixing after air-dry, remove mixture in stone, Levigate 80-100 mesh sieves excessively are standby after the debris such as grass cuttings;
(5)By cladding alkali miberal powder end, step 3 gained composite powder and step 4 gained compound obtained by step 1 in mass ratio (3-4):(2-4):(10-12)It is granulated in mixing input comminutor, gained particle is renovation agent of the present invention.
2. the preparation method of copper mine soil-repairing agent according to claim 1, it is characterised in that the alkali ore is white Any one in marble, aegirine-augite, calcite, potassium feldspar.
3. the preparation method of copper mine soil-repairing agent according to claim 1, it is characterised in that in the step 2 thoroughly Pyroxene vibrates 18-24 hours, to remove soluble impurity, afterwards at room temperature using being preceding immersed in 1mol/L salpeter solutions With being used after clear water cleaning, drying.
4. the preparation method of copper mine soil-repairing agent according to claim 1, it is characterised in that in the step 3 Stirred under nitrogen atmosphere speed control is at 180-220 revs/min.
5. the application method of the copper mine soil-repairing agent described in claim any one of 1-4, it is characterised in that by copper mine mountain soil The uniform broadcasting of earth renovation agent carries out ploughing soil, the wherein amount of application of renovation agent is soil matter on copper mine contaminated soil surface The 4-8% of amount, repair time are 30-60 days.
CN201710822668.8A 2017-09-13 2017-09-13 A kind of copper mine soil-repairing agent and preparation method thereof Pending CN107674682A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485670A (en) * 2018-03-12 2018-09-04 秋晓东 A kind of nano ecological renovation agent and its renovation technique to heavy-metal contaminated soil
CN114478080A (en) * 2022-02-24 2022-05-13 云南应发生物科技有限公司 Process for manufacturing high-quality high-efficiency silicon fertilizer by using copper-selecting tailing slag
CN115885806A (en) * 2022-09-14 2023-04-04 北京师范大学 Substitute surface soil material for land reclamation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105802637A (en) * 2016-05-03 2016-07-27 四川施利旺农业科技开发有限公司 Soil heavy metal passivator, preparation method thereof, and passivation method thereof on soil cadmium
CN106800939A (en) * 2016-12-26 2017-06-06 四川省有色冶金研究院有限公司 Renovation agent and preparation method thereof for administering soil heavy metal combined pollution

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105802637A (en) * 2016-05-03 2016-07-27 四川施利旺农业科技开发有限公司 Soil heavy metal passivator, preparation method thereof, and passivation method thereof on soil cadmium
CN106800939A (en) * 2016-12-26 2017-06-06 四川省有色冶金研究院有限公司 Renovation agent and preparation method thereof for administering soil heavy metal combined pollution

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485670A (en) * 2018-03-12 2018-09-04 秋晓东 A kind of nano ecological renovation agent and its renovation technique to heavy-metal contaminated soil
CN114478080A (en) * 2022-02-24 2022-05-13 云南应发生物科技有限公司 Process for manufacturing high-quality high-efficiency silicon fertilizer by using copper-selecting tailing slag
CN115885806A (en) * 2022-09-14 2023-04-04 北京师范大学 Substitute surface soil material for land reclamation

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Application publication date: 20180209

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