GB2499867A - Double-layer permeable reactive barrier remediation system - Google Patents
Double-layer permeable reactive barrier remediation system Download PDFInfo
- Publication number
- GB2499867A GB2499867A GB1219329.8A GB201219329A GB2499867A GB 2499867 A GB2499867 A GB 2499867A GB 201219329 A GB201219329 A GB 201219329A GB 2499867 A GB2499867 A GB 2499867A
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- United Kingdom
- Prior art keywords
- reactive barrier
- barrier
- reductive
- oxidative
- double
- Prior art date
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- 230000004888 barrier function Effects 0.000 title claims abstract description 143
- 238000005067 remediation Methods 0.000 title claims abstract description 44
- 230000001590 oxidative effect Effects 0.000 claims abstract description 73
- 230000002829 reductive effect Effects 0.000 claims abstract description 47
- 239000003673 groundwater Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000013268 sustained release Methods 0.000 claims abstract description 30
- 239000012730 sustained-release form Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004343 Calcium peroxide Substances 0.000 claims abstract description 6
- 239000011398 Portland cement Substances 0.000 claims abstract description 6
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 230000035699 permeability Effects 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003344 environmental pollutant Substances 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000003895 groundwater pollution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 2
- 230000036782 biological activation Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/147—Alkali-metal sulfates; Ammonium sulfate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00284—Materials permeable to liquids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00775—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes the composition being used as waste barriers or the like, e.g. compositions used for waste disposal purposes only, but not containing the waste itself
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Soil Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A double-layer permeable reactive barrier remediation system is composed of a reductive reactive barrier (A) and an oxidative reactive barrier (B), wherein the reductive barrier is positioned upstream of the oxidative barrier. Both the reductive and oxidative barriers are constructed in a framed-box structure whose sides comprise mesh. The framed-box structure of the reductive barrier is filled with modified zeolite and zerovalent iron powder, whilst the framed-box structure of the oxidative barrier is filled with sustained-release particles formed by mixing an active oxidant, a stable curable adhesive, zeolite and water. The system is used to remove nitrobenzene from polluted ground water, wherein the upstream reductive barrier reduces the nitrobenzene to produce aniline. The modified zeolite can reduce the production of flocculent precipitate in the reductive barrier body so as to avoid the blockage of the barrier and increase the concentration of Fe2+ in the ground water. The polluted ground water then enters into the oxidative barrier, wherein the aniline is degraded through a catalytic oxidation reaction. Preferably, the active oxidant is a mixture of sodium persulfate and calcium peroxide, whilst the adhesive may be a mixture of Portland cement and fine sands.
Description
DOUBLE-LAYER PERMEABLE REACTIVE BARRIER REMEDIATION SYSTEM AND ITS CONSTRUCTION METHOD AND APPLICATION
Technical Field
5 The invention belongs to a field of prevention and controlling of ground water pollution. Particularly, the invention relates to a double-layer Permeable Reactive Barrier remediation system for use in the remediation of the ground water polluted by nitrobenzene compounds.
10 The invention also relates to a method for constructing the above double-layer Permeable Reactive Barrier remediation system.
The invention also relates to use of the above double-layer Permeable Reactive Barrier remediation system in the remediation of the ground water polluted by 15 nitrobenzene compounds.
Background Art
As one type of the organic pollutants in ground water, nitrobenzene compounds are mainly derived from industrial production processes of detonators, dyes, pesticides, 20 medicaments and organic syntheses, etc., and include nitrobenzene,
nitrochlorobenzene, nitrotoluene, nitrophenol, and the like. The ground water pollution caused by nitrobenzene compounds has become a focus in the field of the prevention and controlling of environmental pollution.
25 Till now, the in situ remediation methods commonly used against nitrobenzene pollutants in ground water include:
1) Fe° reduction, wherein a fixed reactive barrier is usually used, and nitrobenzene compounds are reduced into biodegradable aniline substances by the zerovalent iron powder in the barrier body. The flocculent precipitate and the alkalescent 30 environment generated during the reaction results in the blockage in the barrier i
body and inactivation of the medium material, which is harmful to the degradation of nitrobenzene compounds. In addition, the aniline substances generated through the reaction still have an impact on the quality of ground water.
2) Biological remediation, wherein the biological remediation used against the 5 ground water polluted by nitrobenzene compounds comprises the steps of biological activation and biological reinforcement.
Biological activation is a process of infusing organic carbon and other nutritional ingredients into ground water system, so as to activate indigenous microorganism. This technology is restricted by a disadvantage, i.e. the microorganism which 10 degrades nitrobenzene pollutants in aquifer is in a very small amount. Therefore, its activation accumulation is a slow process, and thus a long remediation period is required.
Biological reinforcement is carried out by infusing allopatric degradation microorganism into ground water system after the microorganism is cultured, 15 acclimatized and loaded. The major disadvantages of this process include the high cost, the difficulty in infusing microorganism into aquifer, and the competition for a limited amount of resources with the in situ microorganism. In addition, because of the flowing of ground water and a weaker affinity between the thalli and the aquifer medium, etc., a severe loss of the reinforced microorganism occurs, so that the 20 effect of the biological remediation is harmed and the cost for the remediation is raised.
Summary of Invention
One object of the invention is to provide a double-layer Permeable Reactive Barrier 25 remediation system.
Another object of the invention is to provide a method for constructing the above double-layer Permeable Reactive Barrier remediation system.
30 In order to achieve the above objects, the invention provides a double-layer
2
Permeable Reactive Barrier remediation system, which is composed of a reductive reactive barrier positioned upstream of water flow and an oxidative reactive barrier positioned downstream of water flow.
5 Both the reductive and oxidative reactive barriers are constructed in a framed-box structure, wherein two surfaces vertical to ground water flow direction and two side surfaces parallel with ground water flow direction of the framed-box structure are equipped with meshes.
10 The meshes of the framed-box structure of the reductive reactive barrier are filled with modified zeolite and zerovalent iron powder, to such an extent that the level of the filled zeolite and iron powder is above the ground water line.
The meshes of the framed-box structure of the oxidative reactive barrier are filled
15 with sustained-release particles formed by mixing an active oxidant, a stable curable adhesive, zeolite and water, to such an extent that the level of the filled sustained-release particles is above the ground water line.
In the double-layer Permeable Reactive Barrier remediation system, the modified
20 zeolite and zerovalent iron powder are in a ratio by mass of 1:0.5-0.9; and the sustained-release particles is prepared by mixing the active oxidant, stable curable adhesive, zeolite and water in a ratio by mass of 1:1.4-1.7: 0.5-0.7: 0.9-1.2 followed by granulation.
25 In the double-layer Permeable Reactive Barrier remediation system, the oxidized sustained-release particles have an average particle size of 4mm; the active oxidant is a mixture of sodium persulfate and calcium peroxide in a ratio by mass of 1:0.05-0.07; and the stable curable adhesive is a mixture of portland cement and fine sands in a ratio by mass of 1:0.13-0.15.
3
The invention also provides a method for constructing the above double-layer Permeable Reactive Barrier remediation system, comprising the steps of
1) digging two channels at the predetermined positions spaced by a distance;
2) producing framed boxes in accordance with the width, depth and thickness 5 of the channels, equipping the two surfaces and the two side surfaces of the framed box with meshes, installing two framed boxes in the channels respectively to allow the two surfaces of the framed box to be vertical to the water flow direction, so as to form the frames of the reductive reactive barrier and the oxidative reactive barrier, wherein the reductive reactive barrier is io positioned upstream of water flow and the oxidative reactive barrier is positioned downstream of water flow; and
3) filling the reductive reactive barrier with mixed modified zeolite and zerovalent iron powder and filling the oxidative reactive barrier with oxidized sustained-release particles, to such an extent that both the level of the mixed
15 modified zeolite and zerovalent iron powder and the level of the oxidized sustained-release particles are above the ground water line, so as to accomplish the installation of the double-layer Permeable Reactive Barrier remediation system.
20 In the method for constructing a double-layer Permeable Reactive Barrier remediation system, the thicknesses of the oxidative reactive barrier and reductive reactive barrier are calculated according to the retention time of water flow and the permeability coefficient of the filling materials; the formula for calculating the thicknesses of the oxidative reactive barrier and reductive reactive barrier is shown 25 as follow:
L=(1-2.5)t*k;
wherein, L represents the thickness of the oxidative reactive barrier or reductive reactive barrier in a unit of meter, t represents the retention time of water flow in a unit of day, and k represents the permeability coefficient of the filling materials in a 30 unit of meter/day.
In the method for constructing a double-layer Permeable Reactive Barrier remediation system, the modified zeolite and zerovalent iron powder are in a ratio by mass of 1:0.5-0.9; and the sustained-release particles is prepared by mixing the 5 active oxidant, stable curable adhesive, zeolite and water in a ratio by mass of 1: 1.4-1.7: 0.5-0.7: 0.9-1.2 followed by granulation.
In the method for constructing a double-layer Permeable Reactive Barrier remediation system, the oxidized sustained-release particles have an average 10 particle size of 4mm; the active oxidant is a mixture of sodium persulfate and calcium peroxide in a ratio by mass of 1:0.05-0.07; and the stable curable adhesive is a mixture of Portland cement and fine sands in a ratio by mass of 1:0.13-0.15.
In the method for constructing a double-layer Permeable Reactive Barrier 15 remediation system, the distance between the reductive reactive barrier and the oxidative reactive barrier is 1.5-5m; and the depths of the reductive reactive barrier and the oxidative reactive barrier are larger than the vertical depth of the pollution plume by 0.5-2.5m.
20 The double-layer Permeable Reactive Barrier remediation system according to the invention can be used for remediating the ground water polluted by nitrobenzene compounds. During the remediation, the oxidative reactive barrier is positioned downstream of water flow. While the ground water polluted by nitrobenzene compounds is flowing through, it was first subjected to a reduction reaction with the 25 zerovalent iron in the reductive reactive barrier so as to produce aniline substances, and the acidic environment generated by the modified zeolite can reduce the production of flocculent precipitate in the barrier body, so as to avoid the blockage of the barrier and increase the concentration of Fe2+ in ground water.
30 After the reduction reaction, the polluted ground water enters into the oxidative
5
reactive barrier. The aniline substances in the ground water are degraded into unpolluted small molecule substances, carbon dioxide and water through a catalytic oxidation reaction with the oxidized sustained-release material under the catalysis of Fe2+, so that nitrobenzene compounds are removed finally.
5
The double-layer Permeable Reactive Barrier remediation system according to the invention has a combined feature of the activated reduction and self-catalyzed oxidation functions, so as to achieve the effective removal of nitrobenzene pollutants in ground water.
10
Description of Drawings
Figure 1 is a schematic diagram showing the structure of the double-layer Permeable Reactive Barrier remediation system according to the invention.
15 Specific Mode for Carrying out the Invention
The double-layer Permeable Reactive Barrier remediation system for use in ground water pollution according to the invention was composed of an anterior reductive reactive barrier upstream consisting of the modified zeolite and zerovalent iron powder and a posterior oxidative reactive barrier downstream filled with 20 sustained-release particles. Nitrobenzene compounds were converted into aniline substances when passing through the reductive reactive barrier, which facilitated further oxidation and removal of pollutants and also provided the catalyzer Fe2+ required for the reaction in the oxidative barrier. A strong oxidant could be sustainedly released from the sustained-release particles of the oxidative reactive 25 barrier, which reduced the erosion rate of the strong oxidant, and avoided the expedited loss of the effective components. The released strong oxidant reacted with aniline substances under the catalysis of Fe2+, by which the aniline substances were degraded into unpolluted small molecule substances, carbon dioxide and water.
6
The remediation system according to the invention was arranged downstream of underground pollution plume of nitrobenzene compounds. The oxidative reactive barrier was installed behind the reductive reactive barrier with a distance of 1.5-5m. The depths of both the reactive barriers were larger than the vertical depth of the
5 pollution plume by 0.5-2.5m. The thickness (L, m) of the Permeable Reactive Barrier could be calculated according to the retention time (t, d) and the permeability coefficient (k, m/d) of the filling materials, based on the formula of L=(1~2.5)t*k.
10 The sustained-release particles filled in the oxidative reactive barrier was produced by mixing the active oxidant, the stable curable adhesive, zeolite and water in a certain ratio followed by granulation. The active oxidant was sodium persulfate and calcium peroxide; and the stable curable adhesive was ordinary portland cement and fine sands.
15
The double-layer Permeable Reactive Barrier remediation system has the following features:
1) Fe2+ can be released in the process of degradation of pollutants in the reductive reactive barrier, which facilitates the generation of strong oxidative
20 radicals in the oxidative reactive barrier, i.e. it catalyzes the persulfate ion released from the solid sustained-release particles in the oxidative reactive barrier;
2) compared with nitrobenzene compounds, their reduction products, i.e., aniline substances are more easily to be degraded and removed by the strong
25 oxidative sustained-release particles in the oxidative reactive barrier; and
3) the low dissolution rate of the oxidant in the oxidative reactive barrier can extend the service life of the system.
30
Based on the investigation in the effects and mechanisms of the reduction and degradation of nitrobenzene compounds and zerovalent iron as well as the
7
oxidation and removal of persulfates, the inventor proposes a double-layer Permeable Reactive Barrier remediation method which has a combined feature of the activated reduction and self-catalyzed oxidation functions, wherein the reductive reactive barrier is positioned ahead of the oxidative reactive barrier, and 5 nitrobenzene compounds can be degraded into aniline substances. During the reaction, Fe2+ released from the reductive barrier sufficiently facilitates the degradation of nitrobenzene compounds caused by the strong oxidant in the oxidative barrier. At the same time, the releasing rate of the effective components of the sustained-release particles in the oxidative reactive barrier is controlled, 10 which extends the service life of the reactive barrier, thereby reducing the frequency for replacement. The detailed process is shown as follows:
(1) based on the investigation in the hydrogeological condition as well as the range and level of the pollution in a target region, the pollution status and transportation trend of nitrobenzene compounds in ground water was predicted simulatively, so as
15 to determine the positions for installing the double-layer Permeable Reactive Barrier;
(2) two channels were dug at the specified positions spaced by a distance of 1.5-5m;
(3) an iron framed box was manufactured in accordance with the widths, depths
20 and thicknesses of the two channels, the two surfaces in the direction of water flow at the left and right sides of the framed box were equipped with iron wire meshes having an aperture of 1mm, the iron framed boxes were installed in the dug channels respectively, so as to form the frames of the reductive reactive barrier A and the oxidative reactive barrier B, as shown in the figure;
25 (4) after the dry, acidic and modified zeolite having a particle size of 1-3mm and zerovalent iron powder were mixed uniformly, the reductive reactive barrier A was filled with the resultant mixture; the oxidative reactive barrier B was filled with oxidized sustained-release particles having a particle size of 3.5-5.0mm. Burnishing was required to be conducted every time when the height of the filling materials 30 was increased by 0.5m; the filling was carried out until the level of the filling
8
materials was higher than ground water line by 0.3-1.5m; as a result, the installation of the double-layer Permeable Reactive Barrier was accomplished; (5) when the ground water polluted by nitrobenzene compounds was flowing through, it was first subjected to a reduction reaction with acidic zeolite and 5 zerovalent iron, so as to produce aniline substances in the reductive reactive barrier, and the acidic environment generated by the modified zeolite reduced the production of flocculent precipitate in the barrier body, so as to avoid the blockage in the reactive barriers and increase the concentration of Fe2+ in ground water; after the reduction reaction, the polluted ground water entered into the oxidative reactive 10 barrier; the aniline substances in the ground water were degraded into unpolluted small molecule substances, carbon dioxide and water through a catalytic oxidation reaction with the oxidized sustained-release material-persulfate ions under the catalysis of Fe2+, so that nitrobenzene compounds were removed finally.
15 EXAMPLES
Example 1:
In a certain site where the ground water was polluted by nitrobenzene, a double-layer Permeable Reactive Barrier was installed following the steps of the 20 invention, based on the investigation in the range and level of the pollution of the ground water in this site. The thicknesses of the two reactive barriers (i.e. the thickness L of the reductive reactive barrier and the thickness L' of the oxidative reactive barrier) were 0.5m and 0.6m respectively, which were calculated in accordance with the formula of L=(1~2.5)t*k. The reductive reactive barrier was 25 filled with a mixture of the modified acidic zeolite and zerovalent iron powder in a ratio by mass of 1:0.5-0.9, The oxidative reactive barrier was filled with oxidized sustained-release particles having an average particle size of 4mm, produced by mixing the active oxidant, the stable curable adhesive, zeolite and water in a ratio of 1:1.5:0.5:1 followed by granulation. Multiple monitoring wells were arranged in 30 the site, and the concentration of the pollutants in the ground water was detected
9
by sampling periodically. The result showed that the concentration of nitrobenzene was decreased from the initial 62.5mg/L to 9.7mg/L and the removal rate was 84.5%, after the whole system run for 120 days.
5 Example 2:
In a certain site where the ground water was polluted by 2,4-dinitrotoluene, a double-layer Permeable Reactive Barrier was installed following the steps of the invention, based on the investigation in the range and level of the pollution of the ground water in this site. The thicknesses of the two reactive barriers, i.e. the 10 thicknesses of the activated reductive permeable reactive barrier and the sustained-release oxidative permeable reactive barrier, were 0.4m and 0.5m respectively, which were calculated in accordance with the formula of L=(1~2.5)t*k. The reductive reactive barrier was filled with a mixture of the modified acidic zeolite and zerovalent iron powder. The oxidative reactive barrier was filled with oxidized 15 sustained-release particles having an average particle size of 4mm, produced by mixing the active oxidant, the stable curable adhesive, zeolite and water in a ratio of 1:1.6:0.5:1.1 followed by granulation. Multiple monitoring wells were arranged in the site, and the concentration of the pollutants in the ground water was detected by sampling periodically. The result showed that the concentration of 20 2,4-dinitrotoluene was decreased from the initial 12.6mg/L to 1.5mg/L and the removal rate was 88.0%, after the whole system run for 90 days.
10
Claims (9)
1. A double-layer Permeable Reactive Barrier remediation system, characterized in that the system is composed of a reductive reactive barrier positioned upstream of 5 water flow and an oxidative reactive barrier positioned downstream of water flow; wherein both the reductive and oxidative reactive barriers are constructed in a framed-box structure, wherein anterior and posterior surfaces vertical to ground water flow direction and two side surfaces parallel with ground water flow 10 direction of the framed-box structure are equipped with meshes;
the meshes of the framed-box structure of the reductive reactive barrier are filled with modified zeolite and zerovalent iron powder, to such an extent that the level of filled zeolite and iron powder is above the ground water line;
the meshes of the framed-box structure of the oxidative reactive barrier are 15 filled with sustained-release particles formed by mixing an active oxidant, a stable curable adhesive, zeolite and water, to such an extent that the level of the filled sustained-release particles is above the ground water line.
2. The double-layer Permeable Reactive Barrier remediation system according to 20 claim 1, wherein the modified zeolite and zerovalent iron powder are in a ratio by mass of 1:0.5-0.9; and the sustained-release particles is prepared by mixing the active oxidant, the stable curable adhesive, zeolite and water in a ratio by mass of 1: 1.4-1.7: 0.5-0.7: 0.9-1.2 followed by granulation.
25
3. The double-layer Permeable Reactive Barrier remediation system according to claim 1, wherein the oxidized sustained-release particles have an average particle size of 4mm; the active oxidant is a mixture of sodium persulfate and calcium peroxide in a ratio by mass of 1:0.05-0.07; and the stable curable adhesive is a mixture of portland cement and fine sands in a ratio by mass of 1:0.13-0.15.
li
4. A method for constructing the double-layer Permeable Reactive Barrier remediation system according to claim 1, comprising the steps of
1) digging two channels at the predetermined positions spaced by a distance;
2) producing framed boxes in accordance with the width, depth and thickness
5 of the channels, equipping the two surfaces and the two side surfaces of the framed box with meshes, installing two framed boxes in the channels respectively to allow the two surfaces of the framed box to be vertical to the water flow direction, so as to form the frames of the reductive reactive barrier and the oxidative reactive barrier, wherein the reductive reactive barrier is 10 positioned upstream of water flow and the oxidative reactive barrier is positioned downstream of water flow; and
3) filling the reductive reactive barrier with mixed modified zeolite and zerovalent iron powder and filling the oxidative reactive barrier with oxidized sustained-release particles, to such an extent that both the levels of the mixed
15 modified zeolite and zerovalent iron powder and the level of the oxidized sustained-release particles are above the ground water line, so as to accomplish the installation of the double-layer Permeable Reactive Barrier remediation system.
20 5. The method for constructing the double-layer Permeable Reactive Barrier remediation system according to claim 4, wherein the thicknesses of the oxidative reactive barrier and reductive reactive barrier are calculated according to the retention time of water flow and the permeability coefficient of the filling materials; the formula for calculating the thicknesses of the oxidative reactive barrier and 25 reductive reactive barrier is shown as follow:
L=(1-2.5)t*k;
wherein, L represents the thickness of the oxidative reactive barrier or reductive reactive barrier in a unit of meter, t represents the retention time of water flow in a unit of day, and k represents the permeability coefficient of the filling materials in a 30 unit of meter/day.
6. The method for constructing the double-layer Permeable Reactive Barrier remediation system according to claim 4, wherein the modified zeolite and zerovalent iron powder are in a ratio by mass of 1:0.5-0.9; and the
5 sustained-release particles is prepared by mixing the active oxidant, stable curable adhesive, zeolite and water in a ratio by mass of 1: 1.4-1.7: 0.5-0.7: 0.9-1.2 followed by granulation.
7. The method for constructing the double-layer Permeable Reactive Barrier 10 remediation system according to claim 4 or 6, wherein the oxidized sustained-release particles have an average particle size of 4mm; the active oxidant is a mixture of sodium persulfate and calcium peroxide in a ratio by mass of 1:0.05-0.07; and the stable curable adhesive is a mixture of portland cement and fine sands in a ratio by mass of 1:0.13-0.15.
15
8. The method for constructing the double-layer Permeable Reactive Barrier remediation system according to claim 4, wherein the distance between the reductive reactive barrier and the oxidative reactive barrier is 1.5-5m; and the depths of the reductive reactive barrier and the oxidative reactive barrier are larger
20 than the vertical depth of the pollution plume by 0.5-2.5m.
9. Use of the double-layer Permeable Reactive Barrier remediation system according to claim 1 in the remediation of the ground water polluted by nitrobenzene compounds, wherein the reductive reactive barrier is positioned
25 upstream of water flow and the oxidative reactive barrier is positioned downstream of water flow, and wherein while the ground water polluted by nitrobenzene compounds is flowing through, it was first subjected to a reduction reaction with the modified zeolite and the zerovalent iron in the reductive reactive barrier so as to produce aniline substances, and the acidic environment generated by the modified 30 zeolite can reduce the production of flocculent precipitate in the barrier body, so as
to avoid the blockage of the barrier and increase the concentration of Fe2+ in the ground water;
and after the reduction reaction, the polluted ground water enters into the oxidative reactive barrier, the aniline substances in the ground water are degraded into 5 unpolluted small molecule substances, carbon dioxide and water through a catalytic oxidation reaction with the oxidized sustained-release material under the catalysis of Fe2+, so that nitrobenzene compounds are removed finally.
14
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| GB2499867B (en) | 2014-12-10 |
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