CN106800938A - A kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil and preparation method thereof - Google Patents
A kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil and preparation method thereof Download PDFInfo
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- CN106800938A CN106800938A CN201611197712.2A CN201611197712A CN106800938A CN 106800938 A CN106800938 A CN 106800938A CN 201611197712 A CN201611197712 A CN 201611197712A CN 106800938 A CN106800938 A CN 106800938A
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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)
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- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil, it is made up of the raw material of following weight portion：53 76 parts of red mud, 16 22 parts of zeolite distills appropriate amount of water, 20 30 parts of humus, 24 parts of land plaster, 1.0mol/L NaCl solutions are appropriate, 47 parts of iron chloride, 25 parts of ferrous sulfate, appropriate concentrated ammonia liquor, 24 parts of potassium silicate, 12 parts of magnesium silicate, 25 parts of medical stone, 0.2 1 parts of shitosan.The present invention is combined zeolite with magnetic iron oxide particle, it is prepared for the magnetic zeolite complex with characterization of adsorption, because heavy metal element remains in the secondary pollution problem produced in soil when avoiding conventional treatment, processed with the granulation of red mud particles coat afterwards, reach control sustained release OH‑The effect of ion, reduces red mud free alkali rate of release, is advantageously implemented effective stable curing of heavy metal in soil ion.
Description
Technical field
The invention belongs to heavy metal pollution of soil Treatment process field, relate more specifically to a kind of silicon for rehabilitating soil
Fertile combined soil renovation agent and preparation method thereof.
Background technology
Heavy metal pollution of soil refers to that due to mankind's activity, the content of minor metallic element in soil in soil exceedes
Background value, excess deposition and the too high levels that cause, are referred to as heavy metal pollution of soil.And farmland soil heavy metals pollution has huge
Big harmfulness, heavy metal in soil pollution can not only cause crop production reduction and quality decline, can also be by soil-plant
System, human body is entered through food chain, is detrimental to health and life security.
Red mud is the residue of generation in aluminum oxide production process, and the oxide containing abundant iron, aluminium and calcium can reduce gold
The solubility and bioavilability of category, continual and steady solidification is played by discharging OH ion pair heavy metal in soil, can be made
It is the stabilizing and curing agent of heavy-metal contaminated soil.But, when current red mud is applied to pollution control and restoration of the ecosystem substantially still
Red mud powder directly is utilized, because its free alkali discharges too fast, causes the soil pH rate of climb quickly, to vegetation and the micro- life of soil
Thing causes serious harm.
Luo Huili, Huang Shengsheng et al. are at it《Red mud modified particles repair materials and its steady to the original position of lead Grown In Zinc Contaminated Soil
Fixedization is studied》In one text, using the potential gelling of aluminum oxide industry waste residue-red mud, drum granulating prepares red mud-phosphorus under normal temperature
Composite particles, and it is applied to the stabilisation reparation in situ of lead Grown In Zinc Contaminated Soil, although red mud-phosphorus composite soil prepared by the method
Renovation agent can neutralize the OH of part red mud-, but the accumulation of Soil Phosphorus is easily caused, phosphorus enrichment is asked in causing surface water
Topic.
Humus contains various functional groups, such as carboxyl, alcoholic extract hydroxyl group, phenolic hydroxyl group, carbonyl and methoxyl group, with very high
Reactivity, itself is a kind of hydrophilic colloid, is the macromolecule mixture with negative electrical charge, with faintly acid.Humus leads to
Cross covalent bond, micro-porous adsorption, hydrophobic adsorbent, hydrogen bond, ionic bond, electronics and the absorption mechanism such as give-receive, can with soil in have
Malicious pollutant and its catabolite etc. interact.
Therefore, the present invention is combined zeolite with magnetic iron oxide particle, is prepared for the magnetic zeolite with characterization of adsorption and is answered
It is fit, it is to avoid because heavy metal element remains in the secondary pollution problem produced in soil during conventional treatment, afterwards with it is red
The granulation of mud particles coat is processed, and reaches control sustained release OH-The effect of ion, reduces red mud free alkali rate of release, is conducive to
Realize effective stable curing of heavy metal in soil ion.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil
And preparation method thereof.
A kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil, is made up of the raw material of following weight portion：Red mud 53-
76 parts, zeolite 16-22 parts, appropriate amount of water is distilled, humus 20-30 parts, land plaster 2-4 parts, 1.0mol/L NaCl solutions are appropriate,
Iron chloride 4-7 parts, ferrous sulfate 2-5 parts, appropriate concentrated ammonia liquor, potassium silicate 2-4 parts, magnesium silicate 1-2 parts, medical stone 2-5 parts, shell gathers
It is sugared 0.2-1 parts.
Comprise the following steps that：
（1）The preparation of magnetic zeolite：
1., compound concentration is 1.0mol/L NaCl solutions, is 1 by zeolite and NaCl solution:10 mass ratio, is added thereto to
Zeolite, is placed in 20-40 DEG C of thermostat water bath afterwards, mechanical agitation 2-3 hours, then with distillation water washing, mistake
Filter, drying, grinding obtain final product na-pretreated zeolite；
2., above-mentioned na-pretreated zeolite is added in 3-5 times of distilled water, stirring forms suspension, adds iron chloride, ferrous sulfate
Stirring mixing, is placed in 60-80 DEG C of thermostat water bath and stirs 2-3 hours, arrives concentrated ammonia liquor fast drop while stirring
In suspension system, the pH values of solution are made to be stirred for 10-25 minutes after reaching 11-12, afterwards by reaction system at 60-80 DEG C
It is aged 1-3 hour in thermostat water bath, with distillation water washing black precipitate, is filtered, perseverance is dried under vacuum in 70-90 DEG C
Weight, grinding obtains final product magnetic zeolite；
（2）The preparation of magnetic zeolite/humus composite colloid：
Humus is distilled into water dissolves with 3-5 times and is configured to solution, heated 20-40 minutes in 40-60 DEG C of water-bath, add step
（1）Magnetic zeolite, mechanical agitation 1-3 hours under water bath condition, after being cooled to room temperature, dries, shape under the conditions of being placed in 70-90 DEG C
Into dark brown crystal, grind into powder crosses 50-80 mesh sieves, obtains final product magnetic zeolite/humus composite colloid；
（3）The preparation of modified medical stone：
Medical stone is carried out into calcining 0.5-1 hours at 250-350 DEG C, shitosan stirring reaction is added 1-2 hours, treats that temperature is cooled down
To adding potassium silicate, magnesium silicate to be stirred reaction 2-3 hours during normal temperature, graininess is finally ground to form, cross 800 mesh sieves；
（4）Red mud base modified particles：
1., red mud is placed in calcining furnace, is cooled down after being calcined 20-30 minutes at 200-300 DEG C and taken out, 50- is crossed after crushing
100 mesh sieves, obtain red mud particle standby；
2., by above-mentioned red mud particle, step（2）Magnetic zeolite/humus composite colloid, land plaster mixing, stir 2-4 hours,
Step is added afterwards（3）Modified medical stone continues to stir, and is well mixed all materials, puts mixed powder in granulating disc
In, control granulation rotating speed 20-40r/min, by 0.4-0.6:1 ratio of mud sprays into water, is placed in and balling-up is granulated in comminutor；
（5）By step（4）Gained particle natural air drying 30-40 hours, the green-ball after air-drying afterwards dries 5-7 in 60-80 DEG C
Hour, natural cooling obtains siliceous fertilizer combined soil renovation agent.
Wherein, described siliceous fertilizer combined soil renovation agent is graininess, and it is shaped as the spherical of particle diameter 2- 3mm.
Compared with prior art, the present invention has advantages below：
（1）Zeolite is combined with magnetic iron oxide particle in the present invention, is prepared for the magnetic zeolite complex with characterization of adsorption,
On the one hand make in magnetic zeolite containing more micropore and mesoporous, increase its specific surface area so that the absorption property enhancing of zeolite,
On the other hand its magnetic property can make renovation agent of the present invention after use, can make saturated zeolite from soil by simple magnetic separation process
Separated in earth, it is to avoid because heavy metal element remains in the secondary pollution problem produced in soil, realization during conventional treatment
Zeolite is recycled；Compounded with the humus containing weak acid performance afterwards, obtain the magnetic boiling with various reactivities
Stone/humus composite colloid, can occur complex reaction with metal ion well, suppress the migration of heavy metal, in addition humic
The presence of matter can strengthen catalase activity in crop body, accelerate plant physiology metabolism, promote the growth of plant.
（2）The present invention is carried out magnetic zeolite/humus composite colloid and red mud particle using the potential gelling of red mud
Cladding granulation treatment, can be such that red mud alkaline matter is coated in the lattice of colloidal solid or interstitial void, slow so as to reach control
Release OH-The effect of ion, reduces red mud free alkali rate of release, suppresses the too fast problem of the soil pH rate of climb, retains
The stronger absorption property of red mud raw material, reaches and effectively facilitates the residual form that each form heavy metal in contaminated soil continues to stabilization
Conversion, solves the problems, such as heavy-metal contaminated soil, the purpose of the treatment of wastes with processes of wastes against one another is reached, with application value and Environmental Effect higher
Benefit.
（3）The siliceous fertilizer added in the present invention（Potassium silicate, magnesium silicate）Can form relatively stable with free heavy metal
Silicate is finally adsorbed the filling adsorptions such as very competent medical stone and finally solidifies in soil, reduces heavy metal and lives
Property, prevent crop from absorbing.
Specific embodiment
A kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil, is made up of the raw material of following weight portion：Red mud 68
Part, 20 parts of zeolite distills appropriate amount of water, and 27 parts of humus, 3 parts of land plaster, 1.0mol/L NaCl solutions are appropriate, 6 parts of iron chloride,
4 parts of ferrous sulfate, appropriate concentrated ammonia liquor, 3 parts of potassium silicate, 2 parts of magnesium silicate, 4 parts of medical stone, 0.7 part of shitosan.
Comprise the following steps that：
（1）The preparation of magnetic zeolite：
1., compound concentration is 1.0mol/L NaCl solutions, is 1 by zeolite and NaCl solution:10 mass ratio, is added thereto to
Zeolite, is placed in 30 DEG C of thermostat water bath afterwards, mechanical agitation 2.5 hours, then with distillation water washing, filtering, baking
Dry, grinding obtains final product na-pretreated zeolite；
2., above-mentioned na-pretreated zeolite is added in 4 times of distilled water, stirring forms suspension, adds iron chloride, ferrous sulfate to stir
Mixing is mixed, is placed in 70 DEG C of thermostat water bath and is stirred 2.5 hours, by concentrated ammonia liquor fast drop to suspended substance while stirring
In system, the pH values of solution are made to be stirred for 20 minutes after reaching 11.5, afterwards by reaction system in 70 DEG C of thermostat water bath
Ageing 2 hours, with distillation water washing black precipitate, filtering, in 80 DEG C of the constant weight that is dried under vacuum to, grinding obtains final product magnetic boiling
Stone；
（2）The preparation of magnetic zeolite/humus composite colloid：
Humus is configured to solution with 4 times of distillation water dissolves, is heated 30 minutes in 50 DEG C of water-baths, add step（1）Magnetic
Zeolite, mechanical agitation 2 hours under water bath condition after being cooled to room temperature, are dried under the conditions of being placed in 80 DEG C, form dark brown brilliant
Body, grind into powder crosses 80 mesh sieves, obtains final product magnetic zeolite/humus composite colloid；
（3）The preparation of modified medical stone：
Medical stone is carried out into calcining 0.7 hour at 300 DEG C, shitosan stirring reaction is added 2 hours, when temperature is cooled to normal temperature
Add potassium silicate, magnesium silicate to be stirred reaction 3 hours, finally grind to form graininess, cross 800 mesh sieves；
（4）Red mud base modified particles：
1., red mud is placed in calcining furnace, is cooled down after being calcined 25 minutes at 280 DEG C and taken out, 80 mesh sieves are crossed after crushing, obtained
Red mud particle is standby；
2., by above-mentioned red mud particle, step（2）Magnetic zeolite/humus composite colloid, land plaster mixing, stir 3 hours, it
After add step（3）Modified medical stone continues to stir, and is well mixed all materials, puts mixed powder in granulating disc,
Control granulation rotating speed 40r/min, by 0.5:1 ratio of mud sprays into water, is placed in and balling-up is granulated in comminutor；
（5）By step（4）Gained particle natural air drying 36 hours, the green-ball after air-drying afterwards is dried 6 hours in 70 DEG C, natural
Cooling, obtains siliceous fertilizer combined soil renovation agent.
Wherein, described siliceous fertilizer combined soil renovation agent is graininess, and it is shaped as the spherical of particle diameter 2-3mm.
In order to further illustrate application value of the invention, inventor chooses one piece of heavy-metal contaminated soil and uses this hair
Bright renovation agent carries out the checking of repairing effect, and wherein content of heavy metal lead is 132.12mg/kg.
60 days after reparation, Lead In Soil content is 63.27 mg/kg；90 days after reparation, Lead In Soil content is 21.03
mg/kg。
Claims (3)
1. a kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil, it is characterised in that by the raw material group of following weight portion
Into：Red mud 53-76 parts, zeolite 16-22 parts, distill appropriate amount of water, humus 20-30 parts, land plaster 2-4 parts, 1.0mol/L NaCl
Appropriate solution, iron chloride 4-7 parts, ferrous sulfate 2-5 parts, appropriate concentrated ammonia liquor, potassium silicate 2-4 parts, magnesium silicate 1-2 parts, medical stone
2-5 parts, shitosan 0.2-1 parts.
2. the preparation method of a kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil according to claims 1,
Characterized in that, comprising the following steps that：
（1）The preparation of magnetic zeolite：
1., compound concentration is 1.0mol/L NaCl solutions, is 1 by zeolite and NaCl solution:10 mass ratio, is added thereto to
Zeolite, is placed in 20-40 DEG C of thermostat water bath afterwards, mechanical agitation 2-3 hours, then with distillation water washing, mistake
Filter, drying, grinding obtain final product na-pretreated zeolite；
2., above-mentioned na-pretreated zeolite is added in 3-5 times of distilled water, stirring forms suspension, adds iron chloride, ferrous sulfate
Stirring mixing, is placed in 60-80 DEG C of thermostat water bath and stirs 2-3 hours, arrives concentrated ammonia liquor fast drop while stirring
In suspension system, the pH values of solution are made to be stirred for 10-25 minutes after reaching 11-12, afterwards by reaction system at 60-80 DEG C
It is aged 1-3 hour in thermostat water bath, with distillation water washing black precipitate, is filtered, perseverance is dried under vacuum in 70-90 DEG C
Weight, grinding obtains final product magnetic zeolite；
（2）The preparation of magnetic zeolite/humus composite colloid：
Humus is distilled into water dissolves with 3-5 times and is configured to solution, heated 20-40 minutes in 40-60 DEG C of water-bath, add step
（1）Magnetic zeolite, mechanical agitation 1-3 hours under water bath condition, after being cooled to room temperature, dries, shape under the conditions of being placed in 70-90 DEG C
Into dark brown crystal, grind into powder crosses 50-80 mesh sieves, obtains final product magnetic zeolite/humus composite colloid；
（3）The preparation of modified medical stone：
Medical stone is carried out into calcining 0.5-1 hours at 250-350 DEG C, shitosan stirring reaction is added 1-2 hours, treats that temperature is cooled down
To adding potassium silicate, magnesium silicate to be stirred reaction 2-3 hours during normal temperature, graininess is finally ground to form, cross 800 mesh sieves；
（4）Red mud base modified particles：
1., red mud is placed in calcining furnace, is cooled down after being calcined 20-30 minutes at 200-300 DEG C and taken out, 50- is crossed after crushing
100 mesh sieves, obtain red mud particle standby；
2., by above-mentioned red mud particle, step（2）Magnetic zeolite/humus composite colloid, land plaster mixing, stir 2-4 hours,
Step is added afterwards（3）Modified medical stone continues to stir, and is well mixed all materials, puts mixed powder in granulating disc
In, control granulation rotating speed 20-40r/min, by 0.4-0.6:1 ratio of mud sprays into water, is placed in and balling-up is granulated in comminutor；
（5）By step（4）Gained particle natural air drying 30-40 hours, the green-ball after air-drying afterwards dries 5-7 in 60-80 DEG C
Hour, natural cooling obtains siliceous fertilizer combined soil renovation agent.
3. the preparation method of a kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil according to claims 2,
Characterized in that, described siliceous fertilizer combined soil renovation agent is graininess, it is shaped as the spherical of particle diameter 2- 3mm.
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| CN201611197712.2A CN106800938A (en) | 2016-12-22 | 2016-12-22 | A kind of siliceous fertilizer combined soil renovation agent for rehabilitating soil and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597787A (en) * | 2017-08-11 | 2018-01-19 | 航天凯天环保科技股份有限公司 | A kind of method of waste slag containing mercury efficient stable |
| CN108017075A (en) * | 2017-11-24 | 2018-05-11 | 中南大学 | A kind of method for promoting Bayer process red mud macro aggregate to be formed |
| CN108219794A (en) * | 2017-12-30 | 2018-06-29 | 上海康恒环境修复有限公司 | One kind repairs medicament and application method for Wheat in Northern growing area farmland cadmium pollution soil |
| CN109097052A (en) * | 2018-08-31 | 2018-12-28 | 哈密国家农业科技园区管委会 | A kind of natural medical stone agricultural soil heavy metal deactivator and preparation method thereof |
| CN109332370A (en) * | 2018-11-22 | 2019-02-15 | 东北石油大学 | In-situ remediation method for heavy metal chromium ionic soil soil |
| CN111389897A (en) * | 2020-03-13 | 2020-07-10 | 广东东华园林绿化工程有限公司 | Soil pollution treatment method for ecological environment restoration |
| CN113617820A (en) * | 2021-08-18 | 2021-11-09 | 东华大学 | Passivation method and application of heavy metals in red mud |
| CN113969174A (en) * | 2020-07-22 | 2022-01-25 | 清华大学 | Soil heavy metal pollution repairing agent and preparation method and use method thereof |
| CN115259624A (en) * | 2022-09-06 | 2022-11-01 | 昆明冶金研究院有限公司 | Red mud soil treatment method |
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| CN105316001A (en) * | 2015-11-17 | 2016-02-10 | 中电投山西铝业有限公司 | Red mud particle soil repairing adhesives and preparation method thereof |
| CN105541513A (en) * | 2015-12-16 | 2016-05-04 | 金维典 | Compound multifunctional soil remediation agent and preparation method thereof |
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Patent Citations (2)
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| CN105316001A (en) * | 2015-11-17 | 2016-02-10 | 中电投山西铝业有限公司 | Red mud particle soil repairing adhesives and preparation method thereof |
| CN105541513A (en) * | 2015-12-16 | 2016-05-04 | 金维典 | Compound multifunctional soil remediation agent and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597787A (en) * | 2017-08-11 | 2018-01-19 | 航天凯天环保科技股份有限公司 | A kind of method of waste slag containing mercury efficient stable |
| CN108017075A (en) * | 2017-11-24 | 2018-05-11 | 中南大学 | A kind of method for promoting Bayer process red mud macro aggregate to be formed |
| CN108219794A (en) * | 2017-12-30 | 2018-06-29 | 上海康恒环境修复有限公司 | One kind repairs medicament and application method for Wheat in Northern growing area farmland cadmium pollution soil |
| CN108219794B (en) * | 2017-12-30 | 2023-09-29 | 上海康恒环境修复有限公司 | Pesticide for restoring farmland cadmium-polluted soil in northern wheat planting area and use method |
| CN109097052A (en) * | 2018-08-31 | 2018-12-28 | 哈密国家农业科技园区管委会 | A kind of natural medical stone agricultural soil heavy metal deactivator and preparation method thereof |
| CN109332370A (en) * | 2018-11-22 | 2019-02-15 | 东北石油大学 | In-situ remediation method for heavy metal chromium ionic soil soil |
| CN111389897A (en) * | 2020-03-13 | 2020-07-10 | 广东东华园林绿化工程有限公司 | Soil pollution treatment method for ecological environment restoration |
| CN113969174A (en) * | 2020-07-22 | 2022-01-25 | 清华大学 | Soil heavy metal pollution repairing agent and preparation method and use method thereof |
| CN113617820A (en) * | 2021-08-18 | 2021-11-09 | 东华大学 | Passivation method and application of heavy metals in red mud |
| CN115259624A (en) * | 2022-09-06 | 2022-11-01 | 昆明冶金研究院有限公司 | Red mud soil treatment method |
| CN115259624B (en) * | 2022-09-06 | 2023-12-08 | 昆明冶金研究院有限公司 | Red mud soil treatment method |
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Application publication date: 20170606 |