CN106348419A - Method for polluted wastewater restoration by taking natural pyrrhotite and zero-valent iron as PRB (permeable reactive barrier) active filler - Google Patents
Method for polluted wastewater restoration by taking natural pyrrhotite and zero-valent iron as PRB (permeable reactive barrier) active filler Download PDFInfo
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- CN106348419A CN106348419A CN201610832509.1A CN201610832509A CN106348419A CN 106348419 A CN106348419 A CN 106348419A CN 201610832509 A CN201610832509 A CN 201610832509A CN 106348419 A CN106348419 A CN 106348419A
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- prb
- zero
- heavy metal
- valent iron
- iron ore
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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
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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
-
- 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
-
- 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)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a method for polluted wastewater restoration by taking natural pyrrhotite and zero-valent iron as PRB (permeable reactive barrier) active filler. The method includes steps: (1) adding the filler for heavy metal pollution restoration into a PRB device, wherein the filler is formed by mixing natural pyrrhotite, zero-valent iron and sand according to a certain proportion; (2) collecting wastewater with heavy metal pollutants, and adjusting pH of the wastewater with the heavy metal pollutants to 2-9; (3) adopting a peristaltic pump for injecting the wastewater into the PRB reaction device by a certain flow velocity; (4) sampling at an outlet of the PRB reaction device at a certain time interval, and analytically testing heavy metal ions in samples. According to the method, heavy metal polluted water flowing through the PRB device completely contacts with active materials, and accordingly stability and effectiveness in restoration of underground heavy metal polluted water are realized.
Description
Technical field
The invention belongs to field is repaired in environmental pollution, be related to a kind of using natural magnetic iron ore and zeroth order iron mixture as
The method containing the heavy metal contaminants such as cr (vi), se (vi), se (iv) and u (vi) in prb active filler in-situ remediation of underground water.
Background technology
The development of the industries such as mining, smelting, chemical industry, papermaking makes plurality of heavy metal ion enter through approach such as discharge, seepages
Enter body of groundwater.Research confirms, these heavy metal ion work the mischief to the mankind and vegeto-animal health and lives, or even lead
Lethal die.Therefore, how effectively removably descend water intoxication greatly, the heavy metal contaminants that are difficult metabolism be in the urgent need to address
One of environmental problem.
Groundwater remediation technology includes showering technology (mainly pump-and-treat technology) and based technique for in-situ remediation.Its
In, permeable reaction wall (prb) technology is that one kind is widely used and effective underground pollution water body in-situ recovery technique,
Compared with traditional pump-and-treat technology, it is excellent that this technology has a repairing effect, and without additionaling power, it is excellent that operating cost is cheap etc.
Point, gradually having replaced pump-and-treat technology becomes a kind of main groundwater treatment technology.In general, the activity of filler is to determine
Determine the principal element of prb technology repair ability, be usually used in the active charcoal of filler of prb technology, ion exchange resin, Zero-valent Iron
Deng.Wherein, Zero-valent Iron because its reducing power is strong, raw material is cheap, wide material sources the advantages of, be to process cr in varying environment subsoil water
(vi)、as(v)、as(iii)、cd(ii)、pb(ii)、uo2 2+Deng the most frequently used prb active material of heavy metal contaminants.But,
Zero-valent Iron yet suffers from series of problems as prb active filler, specifically includes that the Zero-valent Iron in (1) body of wall is reducing a huge sum of money
During belonging to ion, the corrosion product such as ferrum (hydrogen) oxide of generation and heavy metal reduzate easily cover zeroth order iron surface
Avtive spot, lead to its reactivity to be remarkably decreased；(2) part Zero-valent Iron is contacted generation gas-evolving electrodes and reacts with water, generates
Precipitated product and hydrogen easily block the duct of materials for wall, thus reducing permeability and the stability of prb.
Natural magnetic iron ore belongs to single sulfide, and chemical composition is fe1-xS, is distributed extensively as dump slag in nature
General.In the case of moistening and air contact, these discarded magnetic iron ore can spontaneous oxidation, produce acid waste water, to subsoil water
Cause serious harm Deng natural environment.Meanwhile, natural magnetic iron ore has the fe of reproducibility2+Ion and negative valency sulphion
(s2-), can be used in the reduction treatment of heavy metal pollution in wastewater thing.And, exist in magnetic iron ore crystalline structure ferrum in debt and
Lead to lower crystal symmetry, thus enhancing the reactivity of magnetic iron ore so as to can have in the range of broader ph
Stronger reducing power.
Therefore, it is used for repairing underground it is proposed that natural magnetic iron ore is mixed with Zero-valent Iron as the active filler of prb
Heavy metal ion in water, to improve the removal effect to pollutant for the prb active filler, improves the operation stability of prb, extends
The service life of prb, thus realize the purpose of " treatment of wastes with processes of wastes against one another ".But up to the present, institute of the present invention employing must utilize natural
The method that magnetic iron ore repairs underground heavy metal-containing waste water with zeroth order iron mixture as prb active filler does not also have document report
Open with patent.
Content of the invention
It is an object of the invention to overcoming underground heavy metal-polluted water rehabilitation cost height common at present, cannot having for a long time
The problems such as effect is processed, there is provided a kind of heavy as prb active filler in-situ immobilization underground with Zero-valent Iron by the use of natural magnetic iron ore
The method of metallic pollution water body, flows through the heavy metal-polluted water of prb and active material is fully contacted, thus reach stable and
Effectively repair the purpose of underground heavy metal-polluted water.
For reaching above-mentioned purpose, the present invention is achieved by the following technical solutions:
Natural magnetic iron ore and the method for zeroth order iron mixture repairing heavy metal pollution waste water, comprise the following steps:
(1) filler being used for repairing heavy metal pollution is loaded in prb device, the natural magnetic that described filler mixes for certain proportion
Pyrite, Zero-valent Iron and sand；Described Zero-valent Iron particle diameter is the iron powder of 80-250 mesh, and spills Zero-valent Iron by washing pickling
Unsalted surface is stand-by；Described natural magnetic iron ore is pulverized by ball mill, and particle diameter is 80-250 mesh, and by washing or pickling
Spill magnetic iron ore unsalted surface stand-by；Described sand is dried with 70 DEG C after adopting ultra-pure water wash clean, and screens particle diameter and be
20-80 mesh；
(2) collect the waste water containing heavy metal contaminants, the ph adjusting heavy metal ion-containing waste water is 2-9；
(3) use peristaltic pump, according to certain flow velocity, waste water is injected prb reaction unit；
(4) sample in prb reaction unit exit at set intervals, the heavy metal ion in sample is analyzed test.
If heavy metal ion-containing waste water ph is between 2-9, do not need to adjust.
Described wriggling flow rate pump is 0.5ml/min-5ml/min.
Described temperature is 4-40 DEG C.
Prb device in described step (1) includes metal ion solution bottle, and described metal ion solution bottle passes through pipe
Road is connected with peristaltic pump, and described peristaltic pump is connected with prb device by pipeline, and described prb device is connected with outflow by pipeline
Liquid bottle.
The method of the natural magnetic iron ore of the present invention and zeroth order iron mixture repairing heavy metal pollution waste water has beneficial as follows
Effect:
1st, natural magnetic iron ore is mixed the removal effect that can improve pollutant as prb filler with Zero-valent Iron；
2nd, gas can be reduced generate, extend the service life of prb；
3rd, natural magnetic iron ore is mining slag, cheap and easy to get, and cost is relatively low, reaches the purpose of " treatment of wastes with processes of wastes against one another " simultaneously.
4th, the device required for reacting is simple, easy to operate, can Continuous Wastewater Treatment, reaction process short it is not necessary to outer
Reagent adding.
Brief description
Fig. 1 is the prb apparatus structure schematic diagram in the present invention；
Wherein, 1 it is solution bottle containing heavy metal ion, 2 be pipeline, 3 be peristaltic pump, 4 be prb device, 5 be effluent bottle；
Fig. 2 is the removal effect of embodiment 1 heavy metal ion；
Fig. 3 is the removal effect of embodiment 2 heavy metal ion；
Fig. 4 is the removal effect of embodiment 3 heavy metal ion；
Fig. 5 is the removal effect of embodiment 4 heavy metal ion.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
As shown in figure 1, the prb device in the present invention includes metal ion solution bottle 1, metal ion solution bottle 1 leads to
Cross pipeline 2 and be connected with peristaltic pump 3, peristaltic pump 3 is connected with prb device 4 by pipeline 2, prb device 4 is connected with stream by pipeline 2
Bottle with liquid-out 5.
Embodiment 1
The present embodiment 1 Zero-valent Iron mix with magnetic iron ore as prb filler process containing cr (vi) waste water (concentration be 30ppm, ph
4.5), sequentially include the following steps:
(1) Zero-valent Iron screens the iron powder that particle diameter is 100-150 mesh, and it is stand-by to spill Zero-valent Iron unsalted surface by washing pickling.
Natural magnetic iron ore is pulverized by ball mill, screening particle diameter is 100-150 mesh, and spills magnetic iron ore by washing or pickling
Unsalted surface is stand-by.Sand is dried with 70 DEG C after adopting ultra-pure water wash clean, and screens particle diameter for 20-80 mesh.
(2) weigh Zero-valent Iron 10g and sand 90g loads in prb device；Weigh magnetic iron ore 10g and sand 90g to load
In prb device；Weigh Zero-valent Iron 10g, magnetic iron ore 10g and sand 80g and load prb device, cr will be contained with peristaltic pump respectively
(vi) waste water is passed through in prb device, and solution flow rate is 0.5ml/min.
(3) sample in each prb reaction unit exit at set intervals, water sample simultaneously filters after membrane filtration through 0.22 μm
Sampling, by the concentration of ultraviolet spectrophotometer (mensure wavelength is 540nm) measurement remnant cr (vi).
Prb device effluent cr as shown in Fig. 2 result shows, after prb plant running 20h, through Zero-valent Iron individual processing
(vi) content steeply rises；Content through cr (vi) in the prb device effluent of magnetic iron ore individual processing in 16h after drastically
Rise；By contrast, after the content through cr (vi) in the prb device effluent of Zero-valent Iron and magnetic iron ore mixed processing is in 42h
Just occur rising.As can be seen here, using magnetic iron ore and zeroth order iron mixture as the active filler of prb, prb pair can be significantly improved
The removal effect of cr (vi).
Embodiment 2
The present embodiment 2 Zero-valent Iron mix with magnetic iron ore as prb filler process containing se (vi) waste water (concentration be 25ppm, ph
5.5), sequentially include the following steps:
(1) Zero-valent Iron screens the iron powder that particle diameter is 150-200 mesh, and it is stand-by to spill Zero-valent Iron unsalted surface by washing pickling.
Natural magnetic iron ore is pulverized by ball mill, screening particle diameter is 150-200 mesh, and spills magnetic iron ore by washing or pickling
Unsalted surface is stand-by.Sand is dried with 70 DEG C after adopting ultra-pure water wash clean, and screens particle diameter for 20-80 mesh.
(2) weigh Zero-valent Iron 5g and sand 95g loads in prb device, weigh magnetic iron ore 10g and sand 90g and load prb
In device, weigh Zero-valent Iron 5g, magnetic iron ore 10g and sand 85g and load in prb device, se (vi) will be contained with peristaltic pump respectively
Waste water is passed through in prb, and solution flow rate is 1ml/min.
(3) sample in prb reaction unit exit at set intervals, water sample is simultaneously adopted after 0.22 μm of filtration membrane filtration
Sample, by the concentration of graphite furnace atomic absorption spectrometry measurement remnant se (vi).
Prb device effluent se as shown in figure 3, result shows, after prb plant running 12h, through Zero-valent Iron individual processing
(vi) content steeply rises；Content through se (vi) in the prb device effluent of magnetic iron ore individual processing in 8h after drastically
Rise；By contrast, after the content through se (vi) in the prb device effluent of Zero-valent Iron and magnetic iron ore mixed processing is in 30h
Just occur rising.As can be seen here, using magnetic iron ore and zeroth order iron mixture as the active filler of prb, prb pair can be significantly improved
The removal effect of se (vi).
Embodiment 3
The present embodiment 3 Zero-valent Iron mix with magnetic iron ore as prb filler process containing u (vi) waste water (concentration be 20ppm, ph
7.5), sequentially include the following steps:
(1) Zero-valent Iron screens the iron powder that particle diameter is 80-120 mesh, and it is stand-by to spill Zero-valent Iron unsalted surface by washing pickling.Will
Natural magnetic iron ore is pulverized by ball mill, and screening particle diameter is 80-120 mesh, and it is new to spill magnetic iron ore by washing or pickling
Fresh surface-ready.Sand is dried with 70 DEG C after adopting ultra-pure water wash clean, and screens particle diameter for 20-80 mesh.
(2) weigh Zero-valent Iron 10g and sand 90g loads in prb device, weigh magnetic iron ore 10g and sand 90g and load
In prb device, weigh Zero-valent Iron 10g, magnetic iron ore 10g and sand 80g and load in prb device, u will be contained with peristaltic pump respectively
(vi) waste water is passed through in prb, and solution flow rate is 0.5 ml/min.
(3) sample in prb reaction unit exit at set intervals, water sample is simultaneously adopted after 0.22 μm of filtration membrane filtration
Sample, by the concentration of ultraviolet-uisible spectrophotometer (mensure wavelength is 578nm) measurement remnant u (vi).
Prb device effluent u as shown in figure 4, result shows, after prb plant running 8h, through Zero-valent Iron individual processing
(vi) content steeply rises；Content through u (vi) in the prb device effluent of magnetic iron ore individual processing in 5h after drastically go up
Rise；By contrast, the content through u (vi) in the prb device effluent of Zero-valent Iron and magnetic iron ore mixed processing just goes out after 24h
Now rise.As can be seen here, using magnetic iron ore and zeroth order iron mixture as the active filler of prb, prb can be significantly improved to u
(vi) removal effect.
Embodiment 4
The present embodiment 4 Zero-valent Iron mix with magnetic iron ore as prb filler process containing se (iv) waste water (concentration be 10ppm, ph
8.5), sequentially include the following steps:
(1) Zero-valent Iron screens the iron powder that particle diameter is 200-250 mesh, and it is stand-by to spill Zero-valent Iron unsalted surface by washing pickling.
Natural magnetic iron ore is pulverized by ball mill, screening particle diameter is 200-250 mesh, and spills magnetic iron ore by washing or pickling
Unsalted surface is stand-by.Sand is dried with 70 DEG C after adopting ultra-pure water wash clean, and screens particle diameter for 20-80 mesh.
(2) weigh Zero-valent Iron 10g and sand 90g loads in prb device, weigh magnetic iron ore 5g and sand 95g and load prb
In device, weigh Zero-valent Iron 10g, magnetic iron ore 15g and sand 85g and load in prb device, se (iv) will be contained with peristaltic pump respectively
Waste water is passed through in prb, and solution flow rate is 0.5ml/min.
(3) sample in prb reaction unit exit at set intervals, water sample is simultaneously adopted after 0.22 μm of filtration membrane filtration
Sample, by the concentration of graphite furnace atomic absorption spectrometry measurement remnant se (iv).
Prb device effluent se as shown in figure 5, result shows, after prb plant running 8h, through Zero-valent Iron individual processing
(iv) content steeply rises；Content through se (iv) in the prb device effluent of magnetic iron ore individual processing in 2h after drastically
Rise；By contrast, after the content through se (iv) in prb device 3 effluent of Zero-valent Iron and magnetic iron ore mixed processing is in 20h
Just occur rising.As can be seen here, using magnetic iron ore and zeroth order iron mixture as the active filler of prb, prb pair can be significantly improved
The removal effect of se (iv).
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
All changes that using this design, the present invention is carried out with unsubstantiality, all should fall into protection scope of the present invention.
Claims (5)
1. natural magnetic iron ore and Zero-valent Iron as prb active filler repair pollutant effluents method it is characterised in that include with
Lower step:
(1) filler being used for repairing heavy metal pollution is loaded in prb device, the natural magnetic that described filler mixes for certain proportion
Pyrite, Zero-valent Iron and sand；Described Zero-valent Iron particle diameter is the iron powder of 80-250 mesh, and spills Zero-valent Iron by washing pickling
Unsalted surface is stand-by；Described natural magnetic iron ore is pulverized by ball mill, and particle diameter is 80-250 mesh, and by washing or pickling
Spill magnetic iron ore unsalted surface stand-by；Described sand is dried with 70 DEG C after adopting ultra-pure water wash clean, and screens particle diameter and be
20-80 mesh；
(2) collect the waste water containing heavy metal contaminants, the ph adjusting heavy metal ion-containing waste water is 2-9；
(3) use peristaltic pump, according to certain flow velocity, waste water is injected prb reaction unit；
(4) sample in prb reaction unit exit at set intervals, the heavy metal ion in sample is analyzed test.
2. the method that natural magnetic iron ore repairs pollutant effluents with Zero-valent Iron as prb active filler as claimed in claim 1, its
It is characterised by: if heavy metal ion-containing waste water ph is between 2-9, do not need to adjust.
3. the method that natural magnetic iron ore repairs pollutant effluents with Zero-valent Iron as prb active filler as claimed in claim 1, its
It is characterised by: described wriggling flow rate pump is 0.5ml/min-5ml/min.
4. the method that natural magnetic iron ore repairs pollutant effluents with Zero-valent Iron as prb active filler as claimed in claim 1, its
It is characterised by: described temperature is 4-40 DEG C.
5. the method that natural magnetic iron ore repairs pollutant effluents with Zero-valent Iron as prb active filler as claimed in claim 1, its
It is characterised by: the prb device in described step (1) includes metal ion solution bottle, described metal ion solution bottle passes through
Pipeline is connected with peristaltic pump, and described peristaltic pump is connected with prb device by pipeline, and described prb device is connected with stream by pipeline
Bottle with liquid-out.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610832509.1A CN106348419B (en) | 2016-09-20 | 2016-09-20 | Method for repairing polluted wastewater by using natural pyrrhotite and zero-valent iron as PRB active filler |
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|---|---|---|---|
| CN201610832509.1A CN106348419B (en) | 2016-09-20 | 2016-09-20 | Method for repairing polluted wastewater by using natural pyrrhotite and zero-valent iron as PRB active filler |
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| CN106348419A true CN106348419A (en) | 2017-01-25 |
| CN106348419B CN106348419B (en) | 2020-04-14 |
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Cited By (4)
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| CN110872138A (en) * | 2018-09-03 | 2020-03-10 | 中国科学院沈阳应用生态研究所 | Method for treating farmland drainage by applying engineering waste as PRB filler |
| CN111847622A (en) * | 2019-04-25 | 2020-10-30 | 株式会社神户制钢所 | Method for removing selenium |
| CN111960569A (en) * | 2020-08-04 | 2020-11-20 | 安徽省环境科学研究院 | Zero-valent iron-based method for treating nitrate in wastewater |
| CN116022901A (en) * | 2021-10-26 | 2023-04-28 | 中国地质大学（北京） | PRB dielectric material for removing hexavalent chromium pollutants |
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| CN116022901A (en) * | 2021-10-26 | 2023-04-28 | 中国地质大学（北京） | PRB dielectric material for removing hexavalent chromium pollutants |
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| Publication number | Publication date |
|---|---|
| CN106348419B (en) | 2020-04-14 |
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