CN106811206A - A kind of red mud base modified particles soil remediation material and preparation method thereof - Google Patents

A kind of red mud base modified particles soil remediation material and preparation method thereof Download PDF

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Publication number
CN106811206A
CN106811206A CN201611197419.6A CN201611197419A CN106811206A CN 106811206 A CN106811206 A CN 106811206A CN 201611197419 A CN201611197419 A CN 201611197419A CN 106811206 A CN106811206 A CN 106811206A
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Prior art keywords
red mud
zeolite
parts
modified particles
base modified
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张瑰
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Hu Zitian
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Hu Zitian
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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
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/165Natural alumino-silicates, e.g. zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009Magnetic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes

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

Abstract

The invention discloses a kind of red mud base modified particles soil remediation material, it is made up of the raw material of following weight portion:50 75 parts of red mud, 13 20 parts of zeolite distills appropriate amount of water, and 18 27 parts of humus, 25 parts of land plaster, 1.0mol/L NaCl solutions are appropriate, 57 parts of iron chloride, 35 parts of ferrous sulfate, appropriate concentrated ammonia liquor.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 OHThe effect of ion, reduces red mud free alkali rate of release, is advantageously implemented effective stable curing of heavy metal in soil ion.

Description

A kind of red mud base modified particles soil remediation material and preparation method thereof
Technical field
The invention belongs to heavy metal pollution of soil Treatment process field, relate more specifically to a kind of red mud base modified particles soil Earth repair materials 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 red mud base modified particles soil remediation material and its preparation Method.
A kind of red mud base modified particles soil remediation material, is made up of the raw material of following weight portion:Red mud 50-75 parts, boiling Stone 13-20 parts, appropriate amount of water is distilled, humus 18-27 parts, land plaster 2-5 parts, 1.0mol/L NaCl solutions are appropriate, iron chloride 5- 7 parts, ferrous sulfate 3-5 parts, appropriate concentrated ammonia liquor.
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)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, All powders are well mixed, mixed powder is put in granulating disc, control granulates 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;
(4)By step(3)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 red mud base modified particles soil remediation material.
Wherein, described red mud base modified particles soil remediation material is graininess, its ball for being shaped as particle diameter 2- 3mm Shape.
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.
Specific embodiment
A kind of red mud base modified particles soil remediation material, is made up of the raw material of following weight portion:65 parts of red mud, zeolite 18 Part, appropriate amount of water is distilled, 23 parts of humus, 4 parts of land plaster, 1.0mol/L NaCl solutions are appropriate, 6 parts of iron chloride, ferrous sulfate 4 Part, appropriate concentrated ammonia liquor.
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)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, make All powders are well mixed, and put mixed powder in granulating disc, and control granulates rotating speed 30r/min, by 0.5:1 water ash Than spraying into water, it is placed in and balling-up is granulated in comminutor;
(4)By step(3)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 red mud base modified particles soil remediation material.
Wherein, described red mud base modified particles soil remediation material is graininess, its ball for being shaped as particle diameter 2-3mm Shape.
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 64.84 mg/kg;90 days after reparation, Lead In Soil content is 21.47 mg/kg。

Claims (3)

1. a kind of red mud base modified particles soil remediation material, it is characterised in that be made up of the raw material of following weight portion:Red mud 50-75 parts, zeolite 13-20 parts, appropriate amount of water is distilled, humus 18-27 parts, land plaster 2-5 parts, 1.0mol/L NaCl solutions are fitted Amount, iron chloride 5-7 parts, ferrous sulfate 3-5 parts, appropriate concentrated ammonia liquor.
2. a kind of preparation method of the red mud base modified particles soil remediation material according to claims 1, its feature exists In 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, filtering, 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)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, All powders are well mixed, mixed powder is put in granulating disc, control granulates 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;
(4)By step(3)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 red mud base modified particles soil remediation material.
3. a kind of preparation method of the red mud base modified particles soil remediation material according to claims 2, its feature exists In described red mud base modified particles soil remediation material is graininess, and it is shaped as the spherical of particle diameter 2- 3mm.
CN201611197419.6A 2016-12-22 2016-12-22 A kind of red mud base modified particles soil remediation material and preparation method thereof Withdrawn CN106811206A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113617820A (en) * 2021-08-18 2021-11-09 东华大学 Passivation method and application of heavy metals in red mud
CN114479874A (en) * 2022-01-28 2022-05-13 山东大学 Red mud-based heavy metal curing agent and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104741076A (en) * 2015-04-03 2015-07-01 中国地质科学院水文地质环境地质研究所 Magnetic zeolite, and preparation method and application thereof
CN105294023A (en) * 2015-11-17 2016-02-03 中山大学 Method for repairing heavy metal-polluted soil by using red mud granular material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104741076A (en) * 2015-04-03 2015-07-01 中国地质科学院水文地质环境地质研究所 Magnetic zeolite, and preparation method and application thereof
CN105294023A (en) * 2015-11-17 2016-02-03 中山大学 Method for repairing heavy metal-polluted soil by using red mud granular material

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113617820A (en) * 2021-08-18 2021-11-09 东华大学 Passivation method and application of heavy metals in red mud
CN114479874A (en) * 2022-01-28 2022-05-13 山东大学 Red mud-based heavy metal curing agent and preparation method and application thereof

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Application publication date: 20170609