WO2024036966A1 - 一种固废堆场复合金属离子控制方法 - Google Patents
一种固废堆场复合金属离子控制方法 Download PDFInfo
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- WO2024036966A1 WO2024036966A1 PCT/CN2023/083727 CN2023083727W WO2024036966A1 WO 2024036966 A1 WO2024036966 A1 WO 2024036966A1 CN 2023083727 W CN2023083727 W CN 2023083727W WO 2024036966 A1 WO2024036966 A1 WO 2024036966A1
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- WIPO (PCT)
- Prior art keywords
- attapulgite
- solid waste
- layer
- mixed layer
- soil
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- 239000002910 solid waste Substances 0.000 title claims abstract description 45
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229960000892 attapulgite Drugs 0.000 claims abstract description 110
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 110
- 239000002689 soil Substances 0.000 claims abstract description 65
- 238000001179 sorption measurement Methods 0.000 claims abstract description 58
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000003673 groundwater Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 29
- 229910001385 heavy metal Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005065 mining Methods 0.000 claims description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 description 15
- 229910052785 arsenic Inorganic materials 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- -1 arsenic ions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
- B01J20/0266—Compounds of S
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Definitions
- the invention relates to a method for controlling composite metal ions in solid waste yards, belonging to the field of metal pollution control in solid waste yards.
- Non-ferrous metal smelting and tailings stockpiling cause metal pollution in surrounding surface water and groundwater.
- copper smelting and copper slag stacking produce Pb 2+ , As 3+ , Zn 2+ , Cu 2+ emissions and water pollution.
- Zinc smelting and Zinc slag accumulation produces Pb 2+ , As 3+ , Zn 2+ , Cu 2+ , In 2+ , Cd 2+ emissions and water pollution.
- Permeable reactive barrier has the advantages of flexible operation and high pollutant interception efficiency. It is widely used to intercept and remove heavy metal ions in surface water, groundwater, and heap leaching leachate, such as nano zero-valent iron, hydroxyapatite, Fillers such as kaolin and coal-fired power plant ash are widely used in PRB systems for scientific research and engineering applications in the removal of radioactivity and heavy metal ions from water.
- the low saturated adsorption capacity of metal ions, poor selective adsorption performance and dissolution loss of filling materials restrict the further promotion and application of the PRB process.
- the simultaneous interception and treatment technology and system construction method for multiple complex heavy metal ions with significantly different environmental geochemical characteristics have not yet been reported.
- Specific and efficient adsorption materials are the guarantee for the high-performance and stable operation of the PRB system, and nanomaterials with large specific surface areas and rich active sites can provide potential technical support for the development and utilization of the PRB system.
- the present invention proposes a composite metal ion control method for solid waste yards, which can achieve stable and efficient interception and removal of harmful metals, with low cost, simple preparation process and strong product stability. , flexible operation, green and environmentally friendly, and has strong technical guidance and practical engineering application significance for the control of composite metal ion water pollution produced in various coal mines and non-ferrous metal smelting and heap leaching processes.
- the present invention provides a composite metal ion control method for solid waste dumps.
- the penetration of nano-based materials is used to fill the solid waste dumps.
- Sexually reactive barriers enable classified control of complex heavy metals in water bodies;
- a permeable adsorption wall around the solid waste dump that can absorb harmful substances in the leachate.
- the top of the permeable adsorption wall is higher than the top of the solid waste dump. If the solid waste dump is set up on a mountain, it only needs to be placed where the solid waste dump is not surrounded by mountains. enveloping outer profile Build a permeable adsorption wall. If there is groundwater below the solid waste dump, the permeable adsorption wall needs to extend underground to the underground aquifer to prevent the leachate from the solid waste dump from flowing out with the groundwater;
- the permeable adsorption wall is composed of graded multi-layer permeable reaction barriers filled and compacted, which includes inherent soil layers arranged in the innermost and outer two layers. Between the two inherent soil layers, there are sequentially provided the inherent soil layer and concave soil mixed layer, Intrinsic soil layer and concave soil@manganese dioxide mixed layer, intrinsic soil layer and concave soil@copper sulfide mixed layer; intrinsic soil layer, intrinsic soil layer and concave soil mixed layer, intrinsic soil layer and concave soil@manganese dioxide mixed layer , the thickness of the inherent soil layer and the attapulgite@copper sulfide mixed layer is determined based on the total amount of metal ions in the yard and the saturated adsorption capacity of the adsorbent. The amounts of attapulgite, manganese dioxide and copper sulfide are also obtained from the solid waste pile based on pre-sampling measurements. Regulation of heavy metal content in the field;
- the attapulgite layer mixed layer, attapulgite@manganese dioxide mixed layer and attapulgite@copper sulfide mixed layer are easy to prepare MnO 2 and Cu x S nanoparticles by using attapulgite as the base.
- the attapulgite layer mixed layer realizes Cu 2+ , Zn 2+ , Pb 2+ , Cr 6+ /Cr 3+ , Cd 2+ , Ni 2+ and Mn 2+ metal ions are efficiently adsorbed and intercepted, and the attapulgite@manganese dioxide mixed layer realizes As 3+ metal ions.
- the attapulgite@copper sulfide mixed layer achieves efficient adsorption and interception of Hg 2+ metal ions, achieving hierarchical management and control of complex heavy metal ions in water bodies.
- the inherent soil layer, the inherent soil layer and concave soil mixed layer, the inherent soil layer and concave soil@manganese dioxide mixed layer, the inherent soil layer and concave soil@copper sulfide mixed layer only need to be compacted to construct the permeable adsorption wall.
- Compacted density is: 2.0 ⁇ 3.0g/cm 3 .
- the mass ratio of attapulgite to manganese dioxide in attapulgite@manganese dioxide is: (10 ⁇ 1):1.
- Attapulgite and generated manganese dioxide dissolve 145.6g ⁇ 364g of potassium permanganate solid particles in 1500mL of deionized water, and then add 900g ⁇ 500g of potassium permanganate solid particles to the dissolved potassium permanganate solution.
- the potassium permanganate solution added with attapulgite is fully stirred and then subjected to ultrasonic treatment for 40 minutes, so that the added attapulgite can fully absorb manganese ions;
- the mass ratio of attapulgite to copper sulfide in attapulgite@copper sulfide is: (10 ⁇ 1):1
- Attapulgite and generated copper sulfide dissolve 112.5g ⁇ 281.25g copper chloride solid particles in 1000mL deionized water to obtain a copper chloride solution, and add 900g ⁇ 500g attapulgite to the copper chloride solution , to join
- the potassium permanganate solution containing attapulgite is fully stirred and then ultrasonic treated for 40 minutes so that the added attapulgite can fully absorb copper ions;
- This method aims at the composite metal pollution of surrounding surface water and groundwater caused by non-ferrous metal smelting and various types of tailings stockpiling, and develops permeable reaction barriers filled with nano-based materials to achieve classified control of composite heavy metals in water bodies, using cheap and easily available attapulgite
- the substrate is equipped with MnO 2 and Cu x S nanoparticles that are easy to prepare, and through the graded filling of the permeable reaction barrier, Cu 2+ , Zn 2+ , Pb 2+ , Cr 6+ /Cr 3+ , Cd 2+ , respectively Efficient interception of Ni 2+ and Mn 2+ metal ions, and As 3+ and Hg 2+ metal ions.
- a new hierarchical control method for the treatment of complex heavy metal ions in water is proposed, and attapulgite composite MnO 2 and Cu x S nanoparticle materials are used to specifically adsorb As 3+ and Hg 2+ metal ions in water.
- the material preparation is simple and low-cost.
- the complex heavy metal contaminated water treatment process has highly innovative procedures, high metal interception and separation efficiency, low operating costs, and significant scientific research innovation and engineering feasibility.
- Figure 1 is a schematic diagram of the implementation of the composite metal ion control method in the solid waste yard of the present invention
- Figure 2 is a schematic diagram comparing the interception of heavy metal ions in water by attapulgite
- Figure 3 is a photo of the micromorphology of attapulgite (a), nano-MnO 2 particles (b) and attapulgite@MnO 2 material (c);
- Figure 4 is a graph of the saturated adsorption capacity of attapulgite for arsenic ions in water
- Figure 5 is a photo of the micromorphology of attapulgite (a), nano-Cu x S particles (b) and attapulgite@Cu x S material (c);
- Figure 6 is a graph of the saturated adsorption capacity of attapulgite for Hg 2+ in water
- Figure 7 is a histogram of the selective adsorption of multi-metal ions in the water body of the attapulgite@Cu x S material.
- Figure 1 shows a method for controlling composite metal ions in solid waste dumps.
- a permeable reaction barrier filled with nano-based materials is used to control composite heavy metals in water. Classified management and control;
- a permeable adsorption wall is constructed on the outer side of the enclosure. If there is groundwater under the solid waste dump, the permeable adsorption wall needs to extend underground to the underground aquifer to prevent the leachate from the solid waste dump from flowing out with the groundwater;
- the permeable adsorption wall is composed of graded multi-layer permeable reaction barriers filled and compacted, which includes inherent soil layers arranged in the innermost and outer two layers. Between the two inherent soil layers, there are sequentially provided the inherent soil layer and concave soil mixed layer, Intrinsic soil layer and concave soil@manganese dioxide mixed layer, intrinsic soil layer and concave soil@copper sulfide mixed layer; intrinsic soil layer, intrinsic soil layer and concave soil mixed layer, intrinsic soil layer and concave soil@manganese dioxide mixed layer , the thickness of the inherent soil layer and the attapulgite@copper sulfide mixed layer is determined based on the total amount of metal ions in the yard and the saturated adsorption capacity of the adsorbent. The amounts of attapulgite, manganese dioxide and copper sulfide are also obtained from the solid waste pile based on pre-sampling measurements. Regulation of heavy metal content in the field;
- the attapulgite layer mixed layer, attapulgite@manganese dioxide mixed layer and attapulgite@copper sulfide mixed layer are easy to prepare MnO 2 and Cu x S nanoparticles by using attapulgite as the base.
- the attapulgite layer mixed layer realizes Cu 2+ , Zn 2+ , Pb 2+ , Cr 6+ /Cr 3+ , Cd 2+ , Ni 2+ and Mn 2+ metal ions are efficiently adsorbed and intercepted, and the attapulgite@manganese dioxide mixed layer realizes As 3+ metal ions.
- the attapulgite@copper sulfide mixed layer achieves efficient adsorption and interception of Hg 2+ metal ions, achieving hierarchical management and control of complex heavy metal ions in water bodies.
- the inherent soil layer, the inherent soil layer and concave soil mixed layer, the inherent soil layer and concave soil @ manganese dioxide mixed layer, the inherent soil layer and concave soil @ copper sulfide mixed layer only need to be compacted to build the permeable adsorption wall. Density: 2.0 ⁇ 3.0g/cm 3 .
- natural attapulgite can realize Cu 2+ , Zn 2+ , Pb 2+ , Cr 6+ /Cr 3+ , Cd 2+ , Ni 2+ , Mn 2+ metals in water through the interception characteristics of its surface sites. It adsorbs ions, but has no adsorption properties for As 3+ and Hg 2+ in water.
- Attapulgite@ MnO2 preparation Take 3.64g potassium permanganate solid particles, place them in a 500ml beaker, add 125mL deionized water to dissolve, then add 15g attapulgite, stir thoroughly and then ultrasonicate for 40 minutes to make the attapulgite fully absorb manganese ions; weigh 6.58gMnSO 4 ⁇ 2H 2 O (98%) white solid particles are dissolved in 200 mL of deionized water. Use a funnel to add the MnSO4 solution drop by drop. While adding, stir (10r/min) and heat to 150°C (oil bath heating). Add dropwise for 1.0h.
- the micromorphology of the obtained attapulgite@MnO 2 material is shown in Figure 2.
- the saturation adsorption curve of the material for arsenic in water is shown in Figure 3.
- (a) is attapulgite and (b) is Nano-MnO 2 particles
- (c) is the micromorphology of attapulgite@MnO 2 material; as can be seen in Figure 2, attapulgite has more natural rod-like structures, and nano-MnO 2 particles have a particle size of 100 to 200 nm and are in the form of clusters. stacked together. Nano-MnO 2 particles are combined with attapulgite to form attapulgite@MnO 2 materials.
- MnO 2 particles can be evenly embedded on the surface of attapulgite, forming a nano-adsorption material with a large specific surface area and fully exposed MnO 2 active sites.
- the saturation adsorption curve of this material for arsenic in water body shown in Figure 3 shows that the saturated adsorption capacity of arsenic is 10.3mg/L.
- Natural attapulgite does not adsorb arsenic in water, while attapulgite@ MnO2 material can better remove arsenic in water and achieve selective adsorption of arsenic.
- Preparation of materials Preparation of attapulgite@Cu x S. Take 28.125g CuCl 2 solid and place it in a 500mL beaker, add 200mL deionized water to dissolve it, then add 60g attapulgite, stir thoroughly and ultrasonicate for 40 minutes to make the attapulgite fully absorb Cu 2+ ions; use a funnel to add dropwise 101.2 mL of (NH 4 ) 2 S solution was added dropwise while stirring for 1.0 h. After the dropwise addition is completed, continue stirring for 2.0 hours. After stopping stirring, use a vacuum pump to filter the material on a 0.22 ⁇ m water-based filter membrane and dry it in a 40°C oven to obtain the prepared attapulgite @Cu x S material.
- the micromorphology of the obtained attapulgite@MnO 2 material is shown in Figure 4.
- the saturation adsorption curve of the material for mercury in water is shown in Figure 5.
- (a) is attapulgite
- (b) is nano-Cu x S particles
- (c) is attapulgite@Cu x S material. It can be seen from Figure 4 that the nano-Cu x S particles have a particle size of ⁇ 100 nm and are stacked together in clusters, which is not conducive to the interception and adsorption of mercury ions on their surfaces. Nano - Cu x S particles are combined with attapulgite to form attapulgite @ Cu Material.
- the saturated adsorption curve of this material for arsenic in water in Figure 5 shows that the saturated adsorption capacity of mercury is as high as 730 mg/L, which is much higher than natural attapulgite, clay and other minerals, and higher than activated carbon materials. Natural attapulgite has no adsorption effect on mercury in water bodies, while attapulgite @Cu x S particles can better remove mercury in water bodies and achieve selective adsorption of mercury.
- Attapulgite @Cu x S material is used to adsorb and remove Cu 2+ , Zn 2+ , Pb 2+ , Cr 6+ /Cr 3+ , Cd 2+ , Ni 2+ , Mn 2+ , As 3+ and Hg in water
- the results obtained for 2+ complex metal ions are shown in Figure 6. It can be seen that after attapulgite is combined with nano-Cu x S particles, the adsorption performance of Cu 2+ , Zn 2+ , Cr 6+ /Cr 3+ , Cd 2+ , Ni 2+ , and Mn 2+ in the water body is significantly reduced. , but the adsorption performance of Pb 2+ on Hg 2+ is significantly improved. Therefore, the attapulgite@Cu x S material can achieve the specific removal of Hg 2+ in composite heavy metal ions.
- the attapulgite, attapulgite@ MnO2 material, attapulgite @ Cu :500 and 1:200 ratios to build a permeable reaction barrier that intercepts and removes a variety of heavy metal ions.
- the initial concentrations of Cu 2+ , Zn 2+ , Pb 2+ , Cr 6+ /Cr 3+ , Cd 2+ , Ni 2+ , Mn 2+ , As 3+ and Hg 2+ in the leachate are 0.41mg/ L, 0.12mg/L, 0.06mg/L, 0.40mg/L, 0.19mg/L, 0.04 mg/L, 0.54mg/L, 0.08mg/L and 0.2mg/L.
- the concentration of each metal ion is reduced to 0.014mg/L, 0.007mg/L, 0.0mg/L, 0.001mg/L.
Abstract
一种固废堆场复合金属离子控制方法，属于固废堆场金属污染治理领域。在固废堆场周围构建能够吸附渗滤液中有害物质的渗透吸附墙，若固废堆场依靠山体设置，则只需要在固废堆场没有被山体包围的外侧面构筑渗透吸附墙，若固废堆场下方存在地下水，则构筑的渗透吸附墙需要向地下延伸直至地下隔水层，以防止固废堆场的渗滤液随地下水流出；渗透吸附墙顺序由固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层、固有土层构成。
Description
本发明涉及一种固废堆场复合金属离子控制方法，属于固废堆场金属污染治理领域。
有色金属冶炼及尾矿堆存造成周边地表水、地下水金属污染，如铜冶炼与铜渣堆放产生Pb2+、As3+、Zn2+、Cu2+的排放及水体污染，锌的冶炼与锌渣堆放产生Pb2+、As3+、Zn2+、Cu2+、In2+、Cd2+的排放及水体污染，此外煤矿开采及矿坑降雨、尾矿、飞灰、矸石及炉渣堆浸亦会使得有害金属组分进入水体，如煤矸石堆积，形成Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+、As3+及Hg2+复合金属离子的渗滤液，严重制约着矿山绿色开采建设事业发展，给周边生态环境及居民健康带来极大的安全隐患。
渗透性反应屏障(PRB)具有操作灵活、污染物截留效率高的优势，被广泛用于地表水、地下水、堆浸渗滤液中重金属离子的截留去除，如纳米零价铁、羟基磷灰石、高岭土、燃煤电厂灰渣等填料，被广泛地使用于PRB体系用于水体放射性及重金属离子去除的科学研究与工程化应用。但金属离子饱和吸附容量低、选择吸附性能差及填充材料的溶解损耗制约着PRB工艺的进一步推广应用。与此同时，针对环境地球化学特性差异显著的多种复合重金属离子的同步截留治理技术与体系的构建方法，尚未见报道。
专性、高效吸附材料是PRB体系高性能稳定运行的保障，而具有比表面积大、活性位点丰富的纳米材料可为PRB体系的开发利用提供潜在技术支撑。受限于纳米颗粒合成制备成本高、易流失、专性吸附性能差的问题，纳米材料在PRB体系的成功实施案例较少。如何提高纳米材料专性吸附性能与饱和吸附容量、降低制备成本及其稳定性，是亟待解决的科研与工程技术难题。
发明内容
技术问题：本发明针对现有存在的技术问题，提出了一种固废堆场复合金属离子控制方法，能够实现有害金属的稳定、高效截留去除，成本低，制备工艺过程简单、产品稳定性强、操作灵活、绿色环保，对各类煤矿及有色金属冶炼、堆浸过程产生的复合金属离子水污染控制有较强的技术指导与实际工程应用意义。
技术方案：为了达到上述目的，本发明的一种固废堆场复合金属离子控制方法，针对设置在地表的煤与各类金属矿开采过程产生的固废堆场，使用纳米基材料填充的渗透性反应屏障实现水体中复合重金属的分类管控；
在固废堆场周围构建能够吸附渗流液中有害物质的渗透吸附墙，渗透吸附墙顶部高于固废堆场顶部；若固废堆场依靠山体设置则只需要在固废堆场没有被山体包围的外侧面构
筑渗透吸附墙，若固废堆场下方存在地下水，则构筑的渗透吸附墙需要向地下延伸直至地下隔水层，以防止固废堆场的渗滤液随地下水流出；
所述渗透吸附墙为分级多层渗透性反应屏障填充压实构成，其包括设置在最内外两层的固有土层，两层固有土层之间顺序设有固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层；固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层的厚度据堆场金属离子总量和吸附剂的饱和吸附容量确定，凹土、二氧化锰以及硫化铜的用量也根据预先采样测量获得固废堆场的重金属含量调节；
其中凹土层混合层、凹土@二氧化锰混合层以及凹土@硫化铜混合层通过凹土为基底搭载易于制取MnO2、CuxS纳米颗粒，凹土层混合层实现Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+及Mn2+金属离子的高效吸附截留，凹土@二氧化锰混合层实现As3+金属离子的高效吸附截留，凹土@硫化铜混合层实现Hg2+金属离子的高效吸附截留，实现水体复合重金属离子治理的分级管控。
进一步，固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层构筑渗透吸附墙只需要压实即可，压实密度为：2.0～3.0g/cm3。
进一步，凹土@二氧化锰中的凹土与二氧化锰的质量比为：(10～1):1。
进一步，每千克凹土@二氧化锰的制备步骤如下：
按照凹土和生成二氧化锰质量比的不同，将145.6g～364g质量的高锰酸钾固体颗粒溶解于1500mL去离子水中，在后再向溶解了高锰酸钾溶液中加入900g～500g的凹土，对加入凹土的高锰酸钾溶液充分搅拌后进行40min的超声处理，使加入的凹土充分吸附锰离子；
称取98％浓度的263g～658g的硫酸锰MnSO4溶解于2L去离子水中获得硫酸锰溶液，然后采用漏斗向加入了凹土的高锰酸钾溶液中滴加硫酸锰溶液，滴加的同时进行10r/min搅拌并继续进行油浴加热至150℃，直至所有硫酸锰溶液滴加完成，继续反应2.0h，将溶液冷却至室温后进行抽滤分离，对分离出的固体部分使用去离子水和无水乙醇交替洗涤3次；
将洗涤后的固体用真空泵抽滤在0.22μm的水系滤膜上并使用60℃的烘箱中烘干，得到的凹土@二氧化锰MnO2。
进一步，凹土@硫化铜中的凹土与硫化铜的质量比为：(10～1):1
进一步，每千克凹土@硫化铜的制备步骤如下：
按照凹土和生成硫化铜质量比的不同，将112.5g～281.25g质量的氯化铜固体颗粒溶解于1000mL去离子水中获得氯化铜溶液，向氯化铜溶液中加入900g～500g的凹土，对加入
了凹土的高锰酸钾溶液充分搅拌后进行40min的超声处理，使加入的凹土充分吸附铜离子；
量取浓度为20～24％的硫化铵(NH4)2S溶液101.2～404.8mL，采用漏斗逐滴将硫化铵溶液边搅拌边向加入了凹土的氯化铜溶液中滴加，直至滴加完成，继续反应2.0h；之后对持续搅拌后的溶液使用0.22μm的水系滤膜进行真空泵抽滤，结束真空泵抽滤后放入40℃的烘箱中烘干，烘干后的材料即为制备的凹土@硫化铜CuxS。
本方法针对有色金属冶炼及各类尾矿堆存造成的周边地表水、地下水复合金属污染，开发纳米基材料填充的渗透性反应屏障实现水体中复合重金属的分类管控，以廉价易得的凹土为基底搭载易于制取MnO2、CuxS纳米颗粒，通过渗透性反应屏障的分级填充，分别实现Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+及Mn2+金属离子，与As3+、Hg2+金属离子的高效截留。提出水体复合重金属离子治理的分级管控新方法，并采用凹土复合MnO2、CuxS纳米颗粒材料专性吸附水体As3+、Hg2+金属离子，材料制备简便、成本低。复合重金属污染水体处理过程工序创新性强，金属截留和分离效率高，运行成本低，具有显著的科研创新性和工程可行性。
图1为本发明固废堆场复合金属离子控制方法的实施示意图；
图2为凹土对水体中重金属离子的截留对比示意图；
图3为凹土(a)、纳米MnO2颗粒(b)及凹土@MnO2材料(c)的微观形貌照片；
图4为凹土对水体中砷离子的饱和吸附容曲线图；
图5为凹土(a)、纳米CuxS颗粒(b)及凹土@CuxS材料(c)的微观形貌照片；
图6为凹土对水体中Hg2+的饱和吸附容量曲线图；
图7为凹土@CuxS材料水体中多金属离子的选择吸附性柱状图。
下面结合附图通过具体实施方式，对本发明作详细描述。
图1为一种固废堆场复合金属离子控制方法，针对设置在地表的煤与各类金属矿开采过程产生的固废堆场，使用纳米基材料填充的渗透性反应屏障实现水体中复合重金属的分类管控；
在固废堆场周围构建能够吸附渗流液中有害物质的渗透吸附墙，渗透吸附墙顶部高于固废堆场顶部；若固废堆场依靠山体设置则只需要在固废堆场没有被山体包围的外侧面构筑渗透吸附墙，若固废堆场下方存在地下水，则构筑的渗透吸附墙需要向地下延伸直至地下隔水层，以防止固废堆场的渗滤液随地下水流出；
所述渗透吸附墙为分级多层渗透性反应屏障填充压实构成，其包括设置在最内外两层的固有土层，两层固有土层之间顺序设有固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层；固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层的厚度据堆场金属离子总量和吸附剂的饱和吸附容量确定，凹土、二氧化锰以及硫化铜的用量也根据预先采样测量获得固废堆场的重金属含量调节；
其中凹土层混合层、凹土@二氧化锰混合层以及凹土@硫化铜混合层通过凹土为基底搭载易于制取MnO2、CuxS纳米颗粒，凹土层混合层实现Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+及Mn2+金属离子的高效吸附截留，凹土@二氧化锰混合层实现As3+金属离子的高效吸附截留，凹土@硫化铜混合层实现Hg2+金属离子的高效吸附截留，实现水体复合重金属离子治理的分级管控。
固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层构筑渗透吸附墙只需要压实即可，压实密度为：2.0～3.0g/cm3。
一、Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+金属离子截留去除：
采用自配模拟废水，以凹土为吸附剂，在废水pH＝5.0，投加量0.03g吸附剂/50mL废水的实验条件下处理初始浓度为4.05,3.27,3.84,4.19,3.98,4.41,3.12mg/L的Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+金属离子废水，吸附时间为2.0h，吸附处理后各金属离子的浓度为分别为0.02,0.48,0.02,0,0,1.85,1.045mg/L，去除效率分别为99.51％，85.3％，99.5％，100％，100％，58.1％，66.5％。实验结果表明，凹土作为一种天然的重金属碱性配位络合界面，对水体中的Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+金属离子具有较好的吸附截留效果。然而，初始浓度为4.75mg/L和1.5mg/L的As3+、Hg2+金属离子吸附处理时，As3+、Hg2+出水浓度分别为4.525mg/L和1.2mg/L，去除效率分别为4.7％与30％，废水中As3+、Hg2+的去除效率较低。由此可知，天然凹土可通过其表面位点的截留特性实现水体Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+金属离子吸附，但对水体中的As3+、Hg2+无吸附特性。
二、As3+截留去除：
材料的制备：凹土@MnO2制备。取3.64g高锰酸钾固体颗粒，置于500ml烧杯中，加125mL去离子水溶解，再加入15g凹土，充分搅拌后超声处理40min，使凹土充分吸附锰离子；称取6.58gMnSO4□2H2O(98％)白色固体颗粒，溶解于200mL去离子水中，采用漏斗逐滴滴加MnSO4溶液，滴加的同时进行搅拌(10r/min)处理并加热至150℃(油浴加热)，滴加1.0h。冷却至室温后进行抽滤分离，用去离子水和无水乙醇交替洗涤3次。将材料用
真空泵抽滤在0.22μm的水系滤膜上并使用60℃的烘箱中烘干，得到所制备的凹土@MnO2材料。
所得的凹土@MnO2材料的微观形貌如图2中所示，该材料对水体中砷的饱和吸附曲线如图3中所示，图3中(a)为凹土、(b)为纳米MnO2颗粒、(c)为凹土@MnO2材料的微观形貌；图2中可以看出，凹土有较多天然的棒状结构，纳米MnO2颗粒粒径100～200nm，呈团簇堆叠在一起。纳米MnO2颗粒与凹土复合，形成凹土@MnO2材料后，MnO2颗粒可较为均匀的镶嵌在凹土表面，形成比表面积大、MnO2活性位点充分暴露的纳米吸附材料。图3中该材料对水体中砷的饱和吸附曲线表明，砷的饱和吸附容量为10.3mg/L。天然凹土对水体中的砷不具有吸附作用，而凹土@MnO2材料可较好的去除水体中的砷，实现砷的选择性吸附。
三、Hg2+截留与去除：
材料的制备：凹土@CuxS制备。取28.125g CuCl2固体置于500mL烧杯中，加入200mL去离子水将其溶解，再加入60g凹土，充分搅拌后超声处理40min，使凹土充分吸附Cu2+离子；采用漏斗逐滴滴加101.2mL(NH4)2S溶液，滴加的同时进行搅拌处理，滴加1.0h。滴加完成后，继续搅拌2.0h，停止搅拌后将材料用真空泵抽滤在0.22μm的水系滤膜上并使用40℃的烘箱中烘干，得到所制备的凹土@CuxS材料。
所得的凹土@MnO2材料的微观形貌如图4中所示，该材料对水体中汞的饱和吸附曲线如图5中所示，(a)为凹土、(b)为纳米CuxS颗粒、(c)为凹土@CuxS材料。从图4中可以看出，纳米CuxS颗粒粒径～100nm，呈团簇堆叠在一起，不利于其表面汞离子的截留吸附。纳米CuxS颗粒与凹土复合，形成凹土@CuxS材料后，CuxS颗粒可较为均匀的镶嵌在凹土表面，形成比表面积大、CuxS活性位点充分暴露的纳米吸附材料。图5中该材料对水体中砷的饱和吸附曲线表明，汞的饱和吸附容量高达730mg/L，远高于天然凹土、粘土等矿物，高于活性炭材料。天然凹土对水体中的汞不具有吸附作用，而凹土@CuxS颗粒可较好的去除水体中的汞，实现汞的选择性吸附。
采用凹土@CuxS材料吸附去除水体中的Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+、As3+及Hg2+复合金属离子所得结果如图6中所示。可以看出，凹土与纳米CuxS颗粒复合后，对水体中Cu2+、Zn2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+的吸附性能显著降低，但对Pb2+于Hg2+的吸附性能显著提高，由此，凹土@CuxS材料可实现复合重金属离子中Hg2+的专性去除。
以山西某粉煤灰堆场产生的多金属复合渗滤液为处理对象，将凹土、凹土@MnO2材料、凹土@CuxS材料与堆场固有土壤，分别按照1:10、1:500及1:200的比例构筑渗透性反应屏障，截留去除多种重金属离子。渗滤液中Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+、Mn2+、As3+及Hg2+的初始浓度分别为0.41mg/L、0.12mg/L、0.06mg/L、0.40mg/L、0.19mg/L、0.04
mg/L、0.54mg/L、0.08mg/L及0.2mg/L，经截留取出后，各金属离子的浓度降低为0.014mg/L、0.007mg/L、0.0mg/L、0.001mg/L、0.001mg/L、0.02mg/L、0.03mg/L、0.001mg/L及0.0mg/L，出水无重金属离子超标现象(满足饮用水中重金属离子排放限值)。有益效果：
Claims (6)
- 一种固废堆场复合金属离子控制方法，其特征在于：针对设置在地表的煤与各类金属矿开采过程产生的固废堆场，使用纳米基材料填充的渗透性反应屏障实现水体中复合重金属的分类管控；在固废堆场周围构建能够吸附渗流液中有害物质的渗透吸附墙，渗透吸附墙顶部高于固废堆场顶部；若固废堆场依靠山体设置则只需要在固废堆场没有被山体包围的外侧面构筑渗透吸附墙，若固废堆场下方存在地下水，则构筑的渗透吸附墙需要向地下延伸直至地下隔水层，以防止固废堆场的渗滤液随地下水流出；所述渗透吸附墙为分级多层渗透性反应屏障填充压实构成，其包括设置在最内外两层的固有土层，两层固有土层之间顺序设有固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层；固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层的厚度据堆场金属离子总量和吸附剂的饱和吸附容量确定，凹土、二氧化锰以及硫化铜的用量也根据预先采样测量获得固废堆场的重金属含量调节；其中凹土层混合层、凹土@二氧化锰混合层以及凹土@硫化铜混合层通过凹土为基底搭载易于制取MnO2、CuxS纳米颗粒，凹土层混合层实现Cu2+、Zn2+、Pb2+、Cr6+/Cr3+、Cd2+、Ni2+及Mn2+金属离子的高效吸附截留，凹土@二氧化锰混合层实现As3+金属离子的高效吸附截留，凹土@硫化铜混合层实现Hg2+金属离子的高效吸附截留，实现水体复合重金属离子治理的分级管控。
- 根据权利要求1所述固废堆场复合金属离子控制方法，其特征在于：固有土层、固有土层与凹土混合层、固有土层与凹土@二氧化锰混合层、固有土层与凹土@硫化铜混合层构筑渗透吸附墙只需要压实即可，压实密度为：2.0～3.0g/cm3。
- 根据权利要求1所述固废堆场复合金属离子控制方法，其特征在于：凹土@二氧化锰中的凹土与二氧化锰的质量比为：(10～1):1。
- 根据权利要求1所述固废堆场复合金属离子控制方法，其特征在于，每千克凹土@二氧化锰的制备步骤如下：按照凹土和生成二氧化锰质量比的不同，将145.6g～364g质量的高锰酸钾固体颗粒溶解于1500mL去离子水中，在后再向溶解了高锰酸钾溶液中加入900g～500g的凹土，对加入凹土的高锰酸钾溶液充分搅拌后进行40min的超声处理，使加入的凹土充分吸附锰离子；称取98％浓度的263g～658g的硫酸锰MnSO4溶解于2L去离子水中获得硫酸锰溶液，然后采用漏斗向加入了凹土的高锰酸钾溶液中滴加硫酸锰溶液，滴加的同时进行10r/min搅拌并继续进行油浴加热至150℃，直至所有硫酸锰溶液滴加完成，继续反应2.0h，将溶 液冷却至室温后进行抽滤分离，对分离出的固体部分使用去离子水和无水乙醇交替洗涤3次；将洗涤后的固体用真空泵抽滤在0.22μm的水系滤膜上并使用60℃的烘箱中烘干，得到的凹土@二氧化锰MnO2。
- 根据权利要求1所述固废堆场复合金属离子控制方法，其特征在于：凹土@硫化铜中的凹土与硫化铜的质量比为：(10～1):1
- 根据权利要求1所述固废堆场复合金属离子控制方法，其特征在于，每千克凹土@硫化铜的制备步骤如下：按照凹土和生成硫化铜质量比的不同，将112.5g～281.25g质量的氯化铜固体颗粒溶解于1000mL去离子水中获得氯化铜溶液，向氯化铜溶液中加入900g～500g的凹土，对加入了凹土的高锰酸钾溶液充分搅拌后进行40min的超声处理，使加入的凹土充分吸附铜离子；量取浓度为20～24％的硫化铵(NH4)2S溶液101.2～404.8mL，采用漏斗逐滴将硫化铵溶液边搅拌边向加入了凹土的氯化铜溶液中滴加，直至滴加完成，继续反应2.0h；之后对持续搅拌后的溶液使用0.22μm的水系滤膜进行真空泵抽滤，结束真空泵抽滤后放入40℃的烘箱中烘干，烘干后的材料即为制备的凹土@硫化铜CuxS。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289494A (zh) * | 2015-11-18 | 2016-02-03 | 中国科学院兰州化学物理研究所 | 一利用凹凸棒石脱色废土制备二氧化锰/碳/凹凸棒纳米复合吸附剂的方法 |
| CN105854787A (zh) * | 2016-04-26 | 2016-08-17 | 北京化工大学 | 一种用于重金属吸附的季铵盐改性凹凸棒石粘土的制备方法 |
| JP2016187801A (ja) * | 2015-03-30 | 2016-11-04 | 大成建設株式会社 | 重金属吸着剤 |
| CN106677226A (zh) * | 2016-11-21 | 2017-05-17 | 北京高能时代环境技术股份有限公司 | 具有修复与垂直阻隔功能的柔性屏障及其制备与应用 |
| US9884771B1 (en) * | 2012-02-17 | 2018-02-06 | Trc Environmental Corporation | Device and method for trapping non-aqueous-phase liquids prior to a permeable reactive barrier for the treatment of contaminated groundwater |
| CN213171564U (zh) * | 2020-05-21 | 2021-05-11 | 天津中联格林科技发展有限公司 | 一种复合低渗透竖向阻隔反应墙 |
| CN113976603A (zh) * | 2021-11-08 | 2022-01-28 | 北京艾孚润德环境科技有限责任公司 | 一种基于多层反应墙技术处理地下水的原位土壤修复工艺 |
| CN116237009A (zh) * | 2022-08-15 | 2023-06-09 | 中国矿业大学 | 一种固废堆场复合金属离子控制方法 |
-
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9884771B1 (en) * | 2012-02-17 | 2018-02-06 | Trc Environmental Corporation | Device and method for trapping non-aqueous-phase liquids prior to a permeable reactive barrier for the treatment of contaminated groundwater |
| JP2016187801A (ja) * | 2015-03-30 | 2016-11-04 | 大成建設株式会社 | 重金属吸着剤 |
| CN105289494A (zh) * | 2015-11-18 | 2016-02-03 | 中国科学院兰州化学物理研究所 | 一利用凹凸棒石脱色废土制备二氧化锰/碳/凹凸棒纳米复合吸附剂的方法 |
| CN105854787A (zh) * | 2016-04-26 | 2016-08-17 | 北京化工大学 | 一种用于重金属吸附的季铵盐改性凹凸棒石粘土的制备方法 |
| CN106677226A (zh) * | 2016-11-21 | 2017-05-17 | 北京高能时代环境技术股份有限公司 | 具有修复与垂直阻隔功能的柔性屏障及其制备与应用 |
| CN213171564U (zh) * | 2020-05-21 | 2021-05-11 | 天津中联格林科技发展有限公司 | 一种复合低渗透竖向阻隔反应墙 |
| CN113976603A (zh) * | 2021-11-08 | 2022-01-28 | 北京艾孚润德环境科技有限责任公司 | 一种基于多层反应墙技术处理地下水的原位土壤修复工艺 |
| CN116237009A (zh) * | 2022-08-15 | 2023-06-09 | 中国矿业大学 | 一种固废堆场复合金属离子控制方法 |
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