CN110451624A - The permeable coefficient tensor material of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH - Google Patents

The permeable coefficient tensor material of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH Download PDF

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CN110451624A
CN110451624A CN201910876883.5A CN201910876883A CN110451624A CN 110451624 A CN110451624 A CN 110451624A CN 201910876883 A CN201910876883 A CN 201910876883A CN 110451624 A CN110451624 A CN 110451624A
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iron
underground water
hexavalent chromium
scope
width
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CN110451624B (en
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贺治国
曾强
钟慧
胡亮
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Central South University
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Central South University
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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
    • B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Soil Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of permeable coefficient tensor materials of repairing hexavalent chromium polluted underground water within the scope of width pH comprising following components raw material: iron-based dielectric material, quartz sand, clay mineral, active carbon；The iron-based dielectric material in an aqueous medium is reacted to obtain with activator by Iron containing silicate minerals at a temperature of 60~100 DEG C.Permeable coefficient tensor material is constructed of permeable coefficient tensor, it can be long lasting for efficient reduction of hexavalent chromium within the scope of the wide pH that pH is 2~12, effectively raise the utilization efficiency of wall dielectric material, and all kinds of dielectric materials are from a wealth of sources, price is cheap and easy to get, cost is significantly reduced, economic benefit is improved.

Description

The permeable coefficient tensor material of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH
Technical field
The present invention relates to a kind of repair materials of pollution of chromium underground water, and in particular to a kind of by iron-based dielectric material collocation stone The composite material of Cr VI in pollution of chromium underground water can be effectively removed made of sand, clay mineral, active carbon etc. for a long time, Belong to environment remediation technical field.
Background technique
Along with expanding economy, underground water pollution of chromium has been increasingly becoming the more serious problem faced, comes Source mainly includes that the excess of the discharge of industrial and mining enterprises' waste water, the stockpiling of waste residue, the supply of polluted surface water and agriculture chemical makes With etc..
Chromium mainly exists in the form of Cr VI and two kinds of trivalent chromium in the water body and soil of pollution, wherein Cr VI toxicity It is 100 times or more of trivalent chromium toxicity, and mobility is also far longer than trivalent chromium.Therefore, it is for trivalent chromium by hexavalent chrome reduction The major way of pollution of chromium reparation.
In existing underground water pollution control mode, permeable coefficient tensor (PRB) technology is a kind of effective underground water in situ Repair mode.Used wall reaction medium material is mainly reductant, such as vulcanized sodium, sodium sulfite, pyrosulfurous acid Sodium and iron-based material etc..Wherein, iron-based material mainly includes Zero-valent Iron, ferriferous oxide, iron sulfide and iron hydroxide etc..Iron Sill is because having the characteristics that being insoluble in water, cheap, from a wealth of sources, strong reducing property and absorption property has become typical chromium dirt Contaminate the dielectric material of PRB in groundwater remediation.But during repairing pollution of chromium underground water, easily because variation of pH value etc. is led It causes iron-based material surface to corrode, forms one layer of reaction protective film, hinder the further progress of reaction, and reaction wall can be made to send out Raw obstruction, makes under the porosity and hydraulic conductivity of reaction medium.Moreover, the pH value of underground water is because there are a large amount of soluble carbons Hydrochlorate and bicarbonate are often in alkalinity, but above-mentioned related iron-based material leads to its reduction because being passivated under alkaline condition It is weakened severely with adsorption capacity.Therefore, for the reparation of pollution of chromium underground water, need to develop it is a kind of it is cheap, be easy to big Amount production, performance is stable and has the active media material of wide pH value application range.
Summary of the invention
For the permeable coefficient tensor material for repairing pollution of chromium underground water in the prior art, the present invention Purpose be intended to provide one kind within the scope of 2~12 width pH can long-time stable efficiently remove Cr VI in pollution of chromium underground water Permeable coefficient tensor material, and the lower cost for material, preparation are simple, easily batch production, lead in pollution of chromium groundwater remediation Domain will have broad application prospects.
In order to achieve the above technical purposes, the present invention provides repairing hexavalent chromium polluted underground water within the scope of a kind of width pH Permeable coefficient tensor material comprising following components raw material: iron-based dielectric material, quartz sand, clay mineral and active carbon；It is described Iron-based dielectric material is reacted at a temperature of 60~100 DEG C by Iron containing silicate minerals with organic acid activator in an aqueous medium It arrives.
Iron-based dielectric material of the invention is to pass through pyroreaction system using Iron containing silicate minerals and organic acid activator At, under activator effect, the iron in ferrosilicate mineral can form ferrous iron complex state precipitating with organic acid activator, and It is supported on silicate mineral, these ferrous iron complex states precipitating can play the role of effective reduction of hexavalent chromium, while discharge grass Trivalent and Cr VI can be complexed in acid group.
Preferred scheme, the Iron containing silicate minerals include biotite, iron aluminium garnet, staurolite, fayalite, At least one of vesuvian, orthoferrosilite, aegirine, hedenbergite, cummingtonite, osannite.Silicate mineral is as carrier The dispersibility of nano ferrous oxalate can be improved, guarantee nano ferrous oxalate high activity.
Preferred scheme, the Iron containing silicate minerals partial size are 45~150 μm.
The liquid-solid ratio of preferred scheme, Iron containing silicate minerals and organic acid activator and water is 3~6mL:1g, iron content silicon Hydrochlorate mineral and organic acid activator mass ratio are 1:2~2:1.
Preferred scheme, the organic acid activator are at least one of oxalic acid, citric acid, tartaric acid, gallic acid.
Preferred scheme, reaction time are 2~48h.
Preferred permeable coefficient tensor material includes following content of component: 1 part of iron-based dielectric material；Quartz sand 0.2~ 0.4 part；0.1~0.3 part of clay mineral；0.2~0.5 part of active carbon.
Preferred scheme, the clay mineral include one in sepiolite, montmorillonite, attapulgite, galapectite and vermiculite Kind is several, and granular size is 45~380 μm.
Preferred scheme, the granular size of the active carbon are 45~380 μm.
Permeable coefficient tensor material of the invention is the mixing of iron-based dielectric material, quartz sand, clay mineral and active carbon Object constructs permeable coefficient tensor as filled media.In permeable coefficient tensor material provided by the invention, iron-based medium material Expect the active medium as hexavalent chrome reduction, while discharging oxalate trivalent and Cr VI can be complexed, is conducive to by clay mine Object and activated carbon adsorption are fixed, and quartz sand is that filled media prevents reaction wall from blocking, and clay mineral and active carbon mainly play absorption The effect of trivalent chromium and Cr VI.A variety of medium synergistic effects can effectively avoid precipitating from generating, while avoiding single wall and being situated between The hardened and blockage problem of material.Simultaneously as preparing activator used in iron-based material process is organic acid, it also can network Metal ion, and then its precipitating under basic conditions is avoided, therefore the composite dielectric materials are under strongly alkaline conditions to chromium dirt Dye underground water still has good repairing effect.
The permeable coefficient tensor that permeable coefficient tensor material provided by the invention is formed, in the range of pH value is 2~12, After reacting 1h, to the removal rate of Cr VI 95% or more.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
The permeable coefficient tensor material of repairing hexavalent chromium polluted underground water provided by the invention, the iron-based medium material of main material Material is simply synthesized by natural minerals, has the characteristics that low in cost, preparation is simple, easily batch production, and other raw material sources Extensively, inexpensively.
The permeable coefficient tensor stability of material of repairing hexavalent chromium polluted underground water provided by the invention is good, when can run Between it is long, and good hexavalent chromium removal efficiency can be all had under the conditions of acid-base property, such as in the range of pH value is 2~12, instead After answering 1h, to the removal rate of Cr VI 95% or more, will have broad application prospects in pollution of chromium groundwater remediation field.
Detailed description of the invention
Fig. 1 is removal capacity of the permeable coefficient tensor material to Cr VI at various ph values.
Fig. 2 is that permeable coefficient tensor simulates rod structure schematic diagram.
Fig. 3 is the experiment effect figure that underground water is repaired in permeable coefficient tensor simulation in case study on implementation 1.
Fig. 4 is the experiment effect figure that underground water is repaired in permeable coefficient tensor simulation in case study on implementation 2.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention It encloses.
Embodiment 1
In following embodiments, used experimental method is conventional method unless otherwise specified；Used material and Chemical reagent unless otherwise specified, is conventional reagent, commercially obtains.
The raw material used are biotite, two oxalic acid hydrates, active carbon, sepiolite and quartz, wherein biotite and Hai Pao The ingredient of stone is as shown in Table 1 and Table 2.
The main component of 1 biotite of table forms
Ingredient SiO2 MgO Al2O3 Fe2O3 K2O
Content (%) 56.85 0.08 10.52 22.91 5.25
The main component of 2 sepiolite of table
Ingredient SiO2 MgO Al2O3 CaO Fe2O3 K2O
Content (%) 82.71 11.46 2.49 2.07 0.97 0.26
The preparation of iron-based dielectric material: being put into beaker after two oxalic acid hydrates of 50g biotite and 80g are mixed, and is added The deionized water of 200mL reacts 3h in 90 DEG C of magnetic agitation water-bath, is iron-based medium after being filtered, washed and drying Material.
It according to mass ratio is 1: 0.3: 0.2: 0.3 by resulting iron-based dielectric material, active carbon, sepiolite and quartz sand After ratio mixing, being packed into internal diameter is the pillar that 25cm height is 100cm, forms the permeable coefficient tensor of simulation.
By peristaltic pump by initial pH be 9, Cr VI initial concentration be 10.6mg/L simulated groundwater lead to from bottom to top Enter reaction wall, detects the hexavalent chromium concentration of reaction wall outlet end liquid under different time, obtained result is as shown in figure 3, result Show after sustained response 29 days, permeable coefficient tensor reaches removal saturation, illustrates the permeability response constructed by the invention Wall can effective repairing hexavalent chromium polluted underground water.
Embodiment 2
The raw material used are iron aluminium garnet, two oxalic acid hydrates, active carbon, montmorillonite and quartz, wherein iron aluminium pomegranate The ingredient of stone and montmorillonite is as shown in Table 3 and Table 4.
The main component of 3 iron aluminium garnet of table forms
Element Al Fe Si O Ca Mg Na
Content (%) 8.95 30.46 17.29 25.54 1.26 2.04 0.04
The main component of 4 montmorillonite of table
The preparation of iron-based dielectric material: two oxalic acid hydrates of 50g iron aluminium garnet and 100g are mixed, are added 200mL's Deionized water reacts 36h in 90 DEG C of magnetic agitation water-bath, is iron-based dielectric material after being filtered, washed and drying.
It according to mass ratio is 1: 0.2: 0.2: 0.4 by resulting iron-based dielectric material, active carbon, montmorillonite and quartz sand After ratio mixing, being packed into internal diameter is the pillar that 25cm height is 100cm, forms the permeable coefficient tensor of simulation.
By peristaltic pump by initial pH be 9, initial hexavalent chromium concentration be 12mg/L simulated groundwater be passed through from bottom to top Reaction wall detects the hexavalent chromium concentration of reaction wall outlet end liquid under different time, and obtained result is as shown in figure 4, result table Bright, after sustained response 36 days, permeable coefficient tensor reaches removal saturation, illustrates the permeable coefficient tensor constructed by the invention It can effective repairing hexavalent chromium polluted underground water.
Embodiment 3
It is operated by embodiment 1, only controlling initial pH is 2,4,6,8,10 or 12, and Cr VI initial concentration is The simulated groundwater of 20mg/L is passed through reaction wall from bottom to top, and the Cr VI for detecting reaction wall outlet end liquid under different time is dense Degree, obtained result are as shown in Figure 1.The result shows that permeable coefficient tensor of the invention has preferable under condition of different pH Remove the effect of Cr VI.

Claims (8)

1. the permeable coefficient tensor material of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH, it is characterised in that:
Including following components raw material: iron-based dielectric material, quartz sand, clay mineral and active carbon；
The iron-based dielectric material is by Iron containing silicate minerals and organic acid activator in an aqueous medium at a temperature of 60~100 DEG C Reaction obtains.
2. the permeability response walling of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH according to claim 1 Material, it is characterised in that: the Iron containing silicate minerals include biotite, iron aluminium garnet, staurolite, fayalite, Fu Shan At least one of stone, orthoferrosilite, aegirine, hedenbergite, cummingtonite, osannite.
3. the permeability response walling of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH according to claim 1 Material, it is characterised in that: the Iron containing silicate minerals partial size is 45~150 μm.
4. the permeability response walling of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH according to claim 1 Material, it is characterised in that: the liquid-solid ratio of Iron containing silicate minerals and organic acid activator and water is 3~6mL:1g, Iron-containing silicate Mineral and organic acid activator mass ratio are 1:2~2:1.
5. the permeability response walling of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH according to claim 4 Material, it is characterised in that: the organic acid activator is at least one of oxalic acid, citric acid, tartaric acid, gallic acid.
6. the permeability response walling of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH according to claim 1 Material, it is characterised in that: the reaction time is 2~48h.
7. according to claim 1~6 within the scope of a kind of described in any item width pH repairing hexavalent chromium polluted underground water permeability Reaction wall material, it is characterised in that: including following content of component:
1 part of iron-based dielectric material；
0.2~0.4 part of quartz sand；
0.1~0.3 part of clay mineral；
0.2~0.5 part of active carbon.
8. the permeability response walling of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH according to claim 7 Material, it is characterised in that: the type of the clay mineral includes one in sepiolite, montmorillonite, attapulgite, galapectite and vermiculite Kind is several, and granular size is 45~380 μm；The granular size of the active carbon is 45~380 μm.
CN201910876883.5A 2019-09-06 2019-09-17 Permeable reaction wall material for repairing hexavalent chromium polluted underground water within wide pH range Active CN110451624B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110980862A (en) * 2019-12-19 2020-04-10 中科元和环保科技有限公司 Iron-modified biochar particles, and preparation method and application thereof
CN111620427A (en) * 2019-12-20 2020-09-04 华中师范大学 In-situ regeneration oxidation coupling permeable reactive barrier process
CN114425305A (en) * 2022-01-25 2022-05-03 中南大学 Mercury adsorption material, preparation method thereof and application thereof in flue gas or solution demercuration
CN115093003A (en) * 2022-07-06 2022-09-23 重庆大学 Method for driving hexavalent chromium to be instantaneously reduced by virtue of limited domain system
CN115400725A (en) * 2022-08-18 2022-11-29 中南大学 Porous clay-based modified biochar composite material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803486A (en) * 2015-04-21 2015-07-29 江苏上田环境修复有限公司 Permeable reactive barrier material for groundwater chromium pollution remediation and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803486A (en) * 2015-04-21 2015-07-29 江苏上田环境修复有限公司 Permeable reactive barrier material for groundwater chromium pollution remediation and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李成五等: "用草酸从粘土矿物中脱铁", 《国外选矿快报》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110980862A (en) * 2019-12-19 2020-04-10 中科元和环保科技有限公司 Iron-modified biochar particles, and preparation method and application thereof
CN111620427A (en) * 2019-12-20 2020-09-04 华中师范大学 In-situ regeneration oxidation coupling permeable reactive barrier process
CN114425305A (en) * 2022-01-25 2022-05-03 中南大学 Mercury adsorption material, preparation method thereof and application thereof in flue gas or solution demercuration
CN115093003A (en) * 2022-07-06 2022-09-23 重庆大学 Method for driving hexavalent chromium to be instantaneously reduced by virtue of limited domain system
CN115093003B (en) * 2022-07-06 2023-06-09 重庆大学 Method for driving hexavalent chromium to be instantaneously reduced by finite field system
CN115400725A (en) * 2022-08-18 2022-11-29 中南大学 Porous clay-based modified biochar composite material and preparation method and application thereof

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