CN110451624B - Permeable reaction wall material for repairing hexavalent chromium polluted underground water within wide pH range - Google Patents
Permeable reaction wall material for repairing hexavalent chromium polluted underground water within wide pH range Download PDFInfo
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- CN110451624B CN110451624B CN201910876883.5A CN201910876883A CN110451624B CN 110451624 B CN110451624 B CN 110451624B CN 201910876883 A CN201910876883 A CN 201910876883A CN 110451624 B CN110451624 B CN 110451624B
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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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
The invention discloses a permeable reactive wall material for repairing hexavalent chromium polluted underground water in a wide pH range, which comprises the following raw materials in parts by weight: iron-based dielectric material, quartz sand, clay mineral and active carbon; the iron-based dielectric material is obtained by reacting iron-containing silicate minerals and an activator in an aqueous medium at the temperature of 60-100 ℃. The permeable reaction wall constructed by the permeable reaction wall material can continuously and efficiently reduce hexavalent chromium for a long time in a wide pH range with the pH value of 2-12, effectively improves the utilization efficiency of wall medium materials, has wide sources of various medium materials and low price, is easy to obtain, obviously reduces the cost, and improves the economic benefit.
Description
Technical Field
The invention relates to a chromium-polluted groundwater restoration material, in particular to a composite material which is prepared by matching an iron-based medium material with quartz sand, clay minerals, activated carbon and the like and can effectively remove hexavalent chromium in chromium-polluted groundwater for a long time, and belongs to the technical field of environmental restoration.
Background
With the development of economy, the chromium pollution of underground water is gradually becoming an increasingly serious problem, and the sources of the chromium pollution mainly comprise the discharge of waste water of industrial and mining enterprises, the stockpiling of waste residues, the supply of polluted surface water, the excessive use of pesticides and fertilizers and the like.
Chromium mainly exists in two forms of hexavalent chromium and trivalent chromium in polluted water and soil, wherein the toxicity of the hexavalent chromium is more than 100 times of that of the trivalent chromium, and the fluidity of the hexavalent chromium is far greater than that of the trivalent chromium. Therefore, the reduction of hexavalent chromium to trivalent chromium is the primary means of chromium pollution remediation.
In the existing groundwater pollution treatment mode, a Permeable Reactive Barrier (PRB) technology is an effective in-situ groundwater remediation mode. The wall reaction medium material is mainly reducing medium, such as sodium sulfide, sodium sulfite, sodium pyrosulfite, iron-based material, etc. The iron-based material mainly comprises zero-valent iron, iron oxide, iron sulfide, iron hydroxide and the like. The iron-based material has the characteristics of being difficult to dissolve in water, low in price, wide in source, strong in reducibility, high in adsorption performance and the like, and is a typical PRB dielectric material in remediation of chromium-polluted underground water. However, in the process of repairing chromium-polluted groundwater, the surface of the iron-based material is easily corroded due to pH change and the like, a reaction protective film is formed, the further progress of the reaction is hindered, and the reaction wall can be blocked, so that the porosity and the hydraulic conductivity of a reaction medium are reduced. Furthermore, groundwater tends to be alkaline in pH due to the presence of large amounts of soluble carbonates and bicarbonates, but the reducing and adsorbing capacity of the associated iron-based materials described above is greatly impaired by passivation under alkaline conditions. Therefore, in order to repair the chromium-contaminated groundwater, it is necessary to develop an active medium material which is cheap, easy to mass-produce, stable in performance and has a wide pH application range.
Disclosure of Invention
Aiming at the technical problems of the permeable reaction wall material for repairing chromium-polluted underground water in the prior art, the invention aims to provide the permeable reaction wall material capable of stably and efficiently removing hexavalent chromium in the chromium-polluted underground water for a long time in a wide pH range of 2-12, and the permeable reaction wall material is low in cost, simple to prepare, easy to produce in batches and wide in application prospect in the field of repairing chromium-polluted underground water.
In order to achieve the technical purpose, the invention provides a permeable reactive barrier material for repairing hexavalent chromium polluted underground water in a wide pH range, which comprises the following raw materials in parts by weight: iron-based dielectric material, quartz sand, clay mineral and active carbon; the iron-based dielectric material is obtained by reacting iron-containing silicate minerals and an organic acid activator in an aqueous medium at the temperature of 60-100 ℃.
The iron-based dielectric material is prepared by high-temperature reaction of iron-containing silicate minerals and an organic acid activator, under the action of the activator, iron in the iron-containing silicate minerals and the organic acid activator can form ferrous iron complex state precipitates which are loaded on the silicate minerals, the ferrous iron complex state precipitates can play a role in effectively reducing hexavalent chromium, and meanwhile, oxalate is released to complex trivalent chromium and hexavalent chromium.
Preferably, the iron-containing silicate mineral comprises at least one of biotite, iron aluminum garnet, crossed stones, fayalite, glauberite, trapezite, neon, calcium iron pyroxene, magnesium iron amphibole and amphibole. The silicate mineral as a carrier can improve the dispersibility of the nano ferrous oxalate and ensure the high activity of the nano ferrous oxalate.
In a preferable scheme, the particle size of the iron-containing silicate mineral is 45-150 mu m.
In a preferable scheme, the liquid-solid ratio of the iron-containing silicate mineral to the organic acid activator and water is 3-6 mL:1g, and the mass ratio of the iron-containing silicate mineral to the organic acid activator is 1: 2-2: 1.
Preferably, the organic acid activator is at least one of oxalic acid, citric acid, tartaric acid and gallic acid.
In a preferable scheme, the reaction time is 2-48 h.
The preferred permeable reactive wall material comprises the following components in parts by mass: 1 part of iron-based dielectric material; 0.2-0.4 part of quartz sand; 0.1-0.3 parts of clay mineral; 0.2-0.5 part of activated carbon.
Preferably, the clay mineral comprises one or more of sepiolite, montmorillonite, attapulgite, halloysite and vermiculite, and the particle size of the clay mineral is 45-380 μm.
In a preferable scheme, the particle size of the activated carbon is 45-380 μm.
The permeable reactive wall material is a mixture of an iron-based medium material, quartz sand, clay minerals and activated carbon, and is used as a filling medium to construct a permeable reactive wall. In the permeable reaction wall material provided by the invention, the iron-based medium material is used as an active medium for reducing hexavalent chromium, oxalate is released at the same time to complex trivalent chromium and hexavalent chromium, so that the iron-based medium material is favorably adsorbed and fixed by clay minerals and active carbon, quartz sand is used as a filling medium to prevent the reaction wall from being blocked, and the clay minerals and the active carbon mainly play a role in adsorbing trivalent chromium and hexavalent chromium. The synergistic effect of multiple media can effectively avoid the generation of sediment, and simultaneously avoid the hardening and blocking problems of a single wall medium material. Meanwhile, the activator used in the process of preparing the iron-based material is organic acid and can complex metal ions, so that the iron-based material is prevented from precipitating under a strong alkali condition, and the composite medium material still has a good repairing effect on chromium-polluted underground water under the strong alkali condition.
The permeable reaction wall formed by the permeable reaction wall material provided by the invention has a hexavalent chromium removal rate of more than 95% after reaction for 1 hour within a pH value range of 2-12.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the main material iron-based dielectric material of the permeable reactive wall material for repairing hexavalent chromium polluted underground water provided by the invention is simply synthesized by natural minerals, and has the characteristics of low cost, simple preparation, easy batch production and the like, and other raw materials have wide sources and are cheap.
The permeable reaction wall material for repairing the hexavalent chromium polluted underground water, provided by the invention, has good stability and long operation time, and can have good hexavalent chromium removal efficiency under the acid-base condition, for example, the removal rate of hexavalent chromium is more than 95% after reaction for 1h within the range of pH value of 2-12, and the permeable reaction wall material has a wide application prospect in the field of repairing chromium polluted underground water.
Drawings
FIG. 1 shows the hexavalent chromium removal performance of the permeable reactive barrier material at different pH values.
FIG. 2 is a schematic diagram of a column simulation of a permeable reactive wall.
Fig. 3 is a graph showing the experimental effect of the simulation restoration of groundwater by the permeable reactive barrier in example 1.
Fig. 4 is a graph showing the experimental effect of the simulation restoration of groundwater by the permeable reactive barrier in example 2.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
In the following examples, unless otherwise specified, all experimental methods used were conventional methods; the materials and chemical reagents used are, unless otherwise specified, conventional reagents and are commercially available.
The raw materials used were biotite, oxalic acid dihydrate, activated carbon, sepiolite and quartz, wherein the components of biotite and sepiolite are shown in tables 1 and 2.
TABLE 1 composition of the major ingredients of biotite
| Composition (I) | SiO2 | MgO | Al2O3 | Fe2O3 | K2O |
| Content (wt.)(％) | 56.85 | 0.08 | 10.52 | 22.91 | 5.25 |
TABLE 2 main components of sepiolite
| Composition (I) | SiO2 | MgO | Al2O3 | CaO | Fe2O3 | K2O |
| Content (%) | 82.71 | 11.46 | 2.49 | 2.07 | 0.97 | 0.26 |
Preparing an iron-based dielectric material: mixing 50g of biotite and 80g of oxalic acid dihydrate, putting the mixture into a beaker, adding 200mL of deionized water, reacting for 3 hours in a magnetic stirring water bath kettle at 90 ℃, and filtering, washing and drying to obtain the iron-based dielectric material.
Mixing the obtained iron-based dielectric material, activated carbon, sepiolite and quartz sand according to the mass ratio of 1: 0.3: 0.2: 0.3, and filling the mixture into a column with the inner diameter of 25cm and the height of 100cm to form a simulated permeable reaction wall.
Simulated underground water with initial pH of 9 and initial concentration of hexavalent chromium of 10.6mg/L is introduced into the reaction wall from bottom to top through the peristaltic pump, the concentration of hexavalent chromium of the liquid at the outlet end of the reaction wall at different times is detected, the obtained result is shown in figure 3, and the result shows that the permeable reaction wall is removed and saturated after continuous reaction for 29 days, which indicates that the permeable reaction wall constructed by the method can effectively repair the underground water polluted by hexavalent chromium.
Example 2
The raw materials used were iron aluminum garnet, oxalic acid dihydrate, activated carbon, montmorillonite and quartz, wherein the compositions of iron aluminum garnet and montmorillonite are shown in tables 3 and 4.
TABLE 3 composition of iron aluminum garnet
| Element(s) | Al | Fe | Si | O | Ca | Mg | Na |
| Content (%) | 8.95 | 30.46 | 17.29 | 25.54 | 1.26 | 2.04 | 0.04 |
TABLE 4 Main Components of montmorillonite
Preparing an iron-based dielectric material: mixing 50g of iron-aluminum garnet and 100g of oxalic acid dihydrate, adding 200mL of deionized water, reacting for 36h in a magnetic stirring water bath kettle at 90 ℃, filtering, washing and drying to obtain the iron-based dielectric material.
Mixing the obtained iron-based dielectric material, activated carbon, montmorillonite and quartz sand according to the mass ratio of 1: 0.2: 0.4, and then filling the mixture into a column with the inner diameter of 25cm and the height of 100cm to form a simulated permeable reaction wall.
The simulated underground water with the initial pH of 9 and the initial hexavalent chromium concentration of 12mg/L is introduced into the reaction wall from bottom to top through the peristaltic pump, the hexavalent chromium concentration of the liquid at the outlet end of the reaction wall at different times is detected, the obtained result is shown in figure 4, and the result shows that the permeable reaction wall is removed and saturated after the continuous reaction lasts for 36 days, which indicates that the permeable reaction wall constructed by the method can effectively repair the underground water polluted by hexavalent chromium.
Example 3
The operation was carried out as in example 1, except that simulated groundwater having an initial pH of 2, 4, 6, 8, 10 or 12 and an initial concentration of hexavalent chromium of 20mg/L was introduced into the reaction wall from below to above, and the concentration of hexavalent chromium in the liquid at the outlet end of the reaction wall at different times was measured, and the results are shown in FIG. 1. The result shows that the permeable reactive barrier of the invention has better effect of removing hexavalent chromium under different pH conditions.
Claims (5)
1. A permeable reactive barrier material for repairing hexavalent chromium polluted groundwater within a wide pH range is characterized in that: comprises the following raw materials: iron-based dielectric material, quartz sand, clay mineral and active carbon;
the iron-based dielectric material is obtained by reacting iron-containing silicate minerals and an organic acid activator in an aqueous medium at the temperature of 60-100 ℃;
the iron-containing silicate mineral comprises at least one of biotite, iron aluminum garnet, crossed stone, fayalite, Phyllanthus, aegonite, neon, Callerotite, magnesian and Naringite;
the liquid-solid ratio of the iron-containing silicate mineral to the organic acid activator to water is 3-6 mL:1g, and the mass ratio of the iron-containing silicate mineral to the organic acid activator is 1: 2-2: 1;
the organic acid activator is at least one of oxalic acid, citric acid, tartaric acid and gallic acid.
2. The permeable reactive barrier material for the remediation of hexavalent chromium contaminated groundwater within a wide pH range according to claim 1, wherein: the particle size of the iron-containing silicate mineral is 45-150 mu m.
3. The permeable reactive barrier material for the remediation of hexavalent chromium contaminated groundwater within a wide pH range according to claim 1, wherein: the reaction time is 2-48 h.
4. The permeable reactive barrier material for repairing hexavalent chromium-polluted groundwater within a wide pH range according to any one of claims 1 to 3, wherein: the adhesive comprises the following components in parts by mass:
1 part of iron-based dielectric material;
0.2-0.4 part of quartz sand;
0.1-0.3 parts of clay mineral;
0.2-0.5 part of activated carbon.
5. The permeable reactive barrier material for the remediation of hexavalent chromium contaminated groundwater within a wide pH range according to claim 4, wherein: the clay mineral types comprise one or more of sepiolite, montmorillonite, attapulgite, halloysite and vermiculite, and the particle size is 45-380 mu m; the particle size of the activated carbon is 45-380 mu m.
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| 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 |
| CN114425305B (en) * | 2022-01-25 | 2023-05-09 | 中南大学 | Mercury adsorption material, preparation method thereof and application thereof in flue gas or solution mercury removal |
| 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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| 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 |
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| 用草酸从粘土矿物中脱铁;李成五等;《国外选矿快报》;19980930;12-15 * |
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