CN113461273B - Nanometer Cu 0 /Fe 0 Water treatment method for dephosphorization of composite porous material - Google Patents
Nanometer Cu 0 /Fe 0 Water treatment method for dephosphorization of composite porous material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000011148 porous material Substances 0.000 title claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000010949 copper Substances 0.000 claims abstract description 81
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 73
- 239000011574 phosphorus Substances 0.000 claims abstract description 73
- 239000010865 sewage Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 12
- 239000011707 mineral Substances 0.000 claims abstract description 12
- 229910001748 carbonate mineral Inorganic materials 0.000 claims abstract description 9
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 9
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract 2
- 238000011049 filling Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000012466 permeate Substances 0.000 claims description 8
- 239000003673 groundwater Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 238000012163 sequencing technique Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 241000530268 Lycaena heteronea Species 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000907663 Siproeta stelenes Species 0.000 description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 230000001360 synchronised effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 241000692870 Inachis io Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001608 iron mineral Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a nano Cu 0 /Fe 0 A water treatment method for dephosphorization of composite porous material relates to the technical field of water treatment, and is to treat nano Cu 0 /Fe 0 Adding the composite porous material into the phosphorus-containing sewage to remove phosphorus in the phosphorus-containing sewage; wherein, nanometer Cu 0 /Fe 0 The composite porous material is obtained by mixing natural iron ore mineral powder and natural copper carbonate mineral powder and roasting the mixture in an oxygen-free atmosphere. The nano Cu prepared by the invention 0 /Fe 0 The composite porous material has larger specific surface area and higher reactivity. Nano Cu 0 /Fe 0 Nano Cu in composite porous material 0 Can promote surface electron transfer to accelerate reaction rate, and further improve nano Fe 0 Can prevent nano Cu from reacting 0 /Fe 0 The nano Cu can be formed by forming a passivation layer on the surface of the composite porous material 0 /Fe 0 The composite porous material is used as a filtering material for deeply treating phosphorus-containing sewage, and the effluent can reach the surface IV water quality standard, thus being a novel nano mineral material。
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a nano Cu 0 /Fe 0 A water treatment method for dephosphorization of a composite porous material.
Background
Along with the social development, the water environment pollution problem is increasingly prominent, phosphorus is the main cause of eutrophication of water bodies, a large amount of phosphorus-containing organic pollutants exist in the water bodies, and the ecological system is generally influenced by the form of reducing dissolved oxygen in the water and the toxicity of the water bodies, so that the human health is endangered. Meanwhile, phosphorus is a precious resource, so that a novel material is synthesized, synchronous removal and recovery of phosphorus in wastewater can be realized, and the method is an effective method for solving phosphorus pollution.
The nano zero-valent iron copper has strong reducibility and adsorptivity, and is a hot concern in the aspects of environmental purification and repair. In the prior art, nano zero-valent iron and copper are usually obtained by reducing iron ions and copper ions by adopting a reducing agent, but the nano iron and copper prepared by the method has lower activity, is easy to agglomerate in the use process, reduces the wastewater treatment effect and limits the application of the nano zero-valent iron and copper in practice.
Chinese patent CN201310043068.3 discloses a dephosphorization method based on nano iron, which is prepared by reducing broken goethite with hydrogen or carbon monoxide at 500-700 deg.c. Chinese patent CN201410063768.3 discloses a method for synchronous denitrification and dephosphorization by synergistic action of nano iron and microorganism, which adopts natural limonite ore to prepare nano iron by high temperature reduction in hydrogen or carbon monoxide atmosphere, and uses nano iron as filler of anaerobic biological filter to treat sewage containing nitrogen and phosphorus, thereby achieving the effect of synchronous denitrification and dephosphorization. Although the two patents adopt hydrogen to reduce and bake natural limonite to prepare nano zero-valent iron, the obtained nano zero-valent iron has higher reactivity, the nano zero-valent iron is easy to corrode and oxidize to form iron hydroxide in the preparation and storage processes due to the strong reducibility of the nano zero-valent iron, the repair efficiency of the nano zero-valent iron is reduced, and the preparation process of the material needs to adopt hydrogen or carbon monoxide to reduce and bake, so that the preparation method is not energy-saving and environment-friendly.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a nano Cu 0 /Fe 0 A water treatment method for dephosphorization of a composite porous material.
The invention provides a nano Cu 0 /Fe 0 The water treatment process of composite porous material to eliminate phosphate includes nanometer Cu 0 /Fe 0 Adding the composite porous material into the phosphorus-containing sewage to remove phosphorus in the phosphorus-containing sewage; wherein, nanometer Cu 0 /Fe 0 The composite porous material is obtained by mixing natural iron ore mineral powder and natural copper carbonate mineral powder and roasting the mixture in an oxygen-free atmosphere.
Preferably, the mass ratio of the natural iron ore mineral powder to the natural copper carbonate mineral powder is 1-3:1.
preferably, the grain diameter of the natural iron ore mineral powder is less than or equal to 0.1mm, wherein the content of Fe is 30-55%; the grain diameter of the natural copper carbonate mineral powder is less than or equal to 0.1mm, wherein the Cu content is 40-70%.
Preferably, the roasting temperature is 800-1200 ℃ and the roasting time is 1-2h.
Preferably, the phosphorus-containing sewage comprises phosphorus-rich river water, phosphorus-rich landscape water, domestic sewage and polluted underground water.
Preferably, when the nano Cu-Cu composite is used for treating phosphorus-rich river water 0 /Fe 0 The composite porous material is filled in a deep water pool in front of a drop dam of a river channel or in a permeable net cage, and the net cage stacks form a permeable dam, so that phosphorus-rich river water permeates and flows through nano Cu 0 /Fe 0 A composite porous material.
Preferably, when the nano Cu-Cu composite is used for treating the phosphorus-rich landscape water body 0 /Fe 0 The composite porous material is filled in the filter tank, and water of the phosphorus-rich landscape water body is conveyed by a pump to enable the water to permeate through the filter tank.
Preferably, when used for treating domestic sewage, nano Cu is used for treating domestic sewage 0 /Fe 0 Filling the composite porous material into a filter tank, and allowing the domestic sewage after the secondary biochemical treatment to permeate through the filter tank;
or nano Cu 0 /Fe 0 Filling the composite porous material into a biological aerated filter, then conveying the domestic sewage after suspended matters are removed by precipitation into the biological aerated filter by a pump, and aerating the bottom, wherein the air-water ratio is 1:1-2;
or nano Cu 0 /Fe 0 Filling the composite porous material into an anaerobic biological filter, then conveying the domestic sewage after removing suspended matters by precipitation into the anaerobic biological filter by a pump, and continuously feeding water for 0.5-2h by adopting sequencing batch operation;
or nano Cu 0 /Fe 0 Filling the composite porous material into the constructed wetland to be used as a matrix of the constructed wetland, and then conveying the domestic sewage after suspended matters are removed by precipitation into the constructed wetland by a pump, wherein continuous operation is adopted;
or nano Cu 0 /Fe 0 The composite porous material is used as a matrix of a sponge city, and the domestic sewage after suspended matters are removed by precipitation is conveyed into the constructed wetland by a pump, so that continuous operation is adopted.
Preferably, for treating contaminated groundwater, trenches are drilled in the contaminated aquifer perpendicular to the groundwater flow direction and nano Cu is applied 0 /Fe 0 The composite porous material is filled into the excavated grooves to form the permeable walls through which water flows.
The nano Cu 0 /Fe 0 After synchronously removing and recovering phosphorus saturation, the composite porous material can be taken out and replaced with new one, and the waste is rich in phosphorus and organic matters and is used for flower nutrient soil or soil improvement.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes natural iron minerals and natural copper carbonate minerals as raw materials, and has the advantages of abundant resources, low price of raw materials, ecology and environmental protection; the nano-structure is easy to realize, and the processing technology is simple; the functional material contains valence-changing elements, can be converted into functional materials with various valence states and structural states, has various mechanisms for removing pollutants, has adsorption, precipitation, catalysis, chemical oxidation and chemical reduction, and can be used as functional materials for synchronously removing and recovering phosphorus.
2. The natural iron minerals and the natural copper carbonate minerals have huge specific surface area, high adsorption, high chemical reaction activity, high thermal decomposition activity and the like, which determine that the processing utilization of the nano minerals is different from the utilization of the traditional resources, and more attention is paid to the exertion and utilization of the nano characteristics of the nano minerals to process the functional materials.
3. The invention adopts the one-step method to prepare the nano Cu 0 /Fe 0 The composite porous material can promote surface electron transfer to accelerate reaction rate after doping another nano metal zero-valent Cu in a nano zero-valent iron system, further improve the reactivity of nano zero-valent iron, and prevent the formation of a passivation layer to a certain extent.
4. Nano Cu 0 /Fe 0 The composite porous material can effectively and synchronously recover and remove phosphorus in water body, while nano Cu 0 /Fe 0 The composite porous material has large specific surface area, high reactivity, and has 3 orders of magnitude higher phosphorus removal efficiency than commercial iron powder, and nano Cu 0 /Fe 0 The efficiency of removing the phosphorus in the solution of the composite porous material is obviously higher than that of nano zero-valent iron prepared by pure natural limonite; nano Cu 0 /Fe 0 The composite porous material is applied to removing phosphorus in water body, and can further improve the removal rate.
5. Nano Cu 0 /Fe 0 In the composite porous material, nano iron and nano copper on the surface of the porous material form a primary cell, so that electrons are promoted to transfer from the nano iron to the nano copper, and FePO is finally produced 4 The nano zero-valent iron can generate a large amount of H in the corrosion process 2 Wrapping in nano Cu 0 And gradually dissociate into hydrogen atoms at nano Cu 0 Under the catalysis of hydrogen atomThe reaction becomes more vigorous so that it is efficient to recover and remove phosphorus simultaneously.
Drawings
FIG. 1 is an SEM image of the malachite of example 1 of the invention; wherein, the scale of each figure is: a is 20 μm, B is 10 μm, C is 5 μm, D is 2 μm;
FIG. 2 shows nano Cu obtained in example 1 of the present invention 0 /Fe 0 SEM images of the composite porous material; wherein, the scale of each figure is: a is 20 μm, B is 10 μm, C is 5 μm, D is 2 μm.
FIG. 3 is an SEM image of the copper blue ore of example 2 of the present invention; wherein, the scale of each figure is: a is 20 μm, B is 10 μm, C is 5 μm, D is 2 μm;
FIG. 4 shows nano Cu obtained in example 2 of the present invention 0 /Fe 0 SEM images of the composite porous material; wherein, the scale of each figure is: a is 20 μm, B is 10 μm, C is 5 μm, D is 1 μm.
Detailed Description
The technical scheme of the invention is described in detail by the following specific examples
Example 1
Nanometer Cu 0 /Fe 0 The preparation method of the composite porous material comprises the following steps:
s1, natural peacock Dan Kuangdan with Cu content of 56% (main chemical component is Cu) 2 (OH) 2 CO 3 ) Crushing and screening to obtain natural malachite powder with the particle size of 0.5-0.8 mm; natural hematite (main chemical component is alpha-Fe) with Fe content of 60% 2 O 3 ) Crushing and screening to obtain natural hematite powder with the particle size of 0.1-0.8 mm;
s2, according to m in mineral powder Peacock powder ：m Hematite powder The mass ratio of (2) is 1:2, mixing the natural malachite powder and the natural hematite powder in proportion to obtain mixed powder;
s3, roasting the mixed powder in a rotary kiln at 800 ℃ for 1h, and naturally cooling to room temperature under the protection of nitrogen to obtain a target product, namely nano Cu 0 /Fe 0 A composite porous material.
The field emission scanning electron microscope of the obtained target product is shown in fig. 1-2, and the natural malachite has a nano structure as can be seen from fig. 1A-D, and the composite material is further nano structured when the natural malachite-mixed natural hematite is roasted under vacuum. From FIGS. 2A-D, it can be seen that nano Cu 0 /Fe 0 The composite porous material exhibits porous structural characteristics with nano-micron crystal particle size and inter-particulate voids.
Through testing, the nano Cu obtained in the embodiment 0 /Fe 0 The magnetic susceptibility of the composite porous material is 3512 multiplied by 10 -7 m 3 Kg, nano Cu 0 /Fe 0 The specific surface area of the composite porous material is 67.6m 2 /g。
Example 2
Nanometer Cu 0 /Fe 0 The preparation method of the composite porous material comprises the following steps:
s1, natural blue copper ore with Cu content of 54 percent (the main chemical component is Cu 2 (OH) 2 CO 3 ) Crushing and screening to obtain natural blue copper ore with the grain diameter of 0.5-0.8 mm; natural limonite with Fe content of 38% (main chemical component is alpha-Fe) 2 O 3 ) Crushing and screening to obtain natural limonite powder with the particle size of 0.1-0.8 mm;
s2, according to m in mineral powder Natural blue copper mineral powder ：m Natural limonite powder The mass ratio of (2) is 1:2, mixing the natural blue copper ore powder and the natural limonite powder according to a proportion to obtain mixed powder;
s3, roasting the mixed powder in a rotary kiln at 1000 ℃ for 1h, and naturally cooling to room temperature under the protection of nitrogen to obtain a target product, namely nano Cu 0 /Fe 0 A composite porous material.
The field emission scanning electron microscope of the obtained target product is shown in figures 3-4, the natural blue copper ore has a nano structure, when the natural blue copper ore mixed with natural limonite is roasted in air, the composite material is further nano structured, and the nano Cu can be seen in figures 4A-D 0 /Fe 0 The composite porous material exhibits porous structural characteristics with nano-micron crystal particle size and inter-particulate voids.
Through testing, the nano Cu obtained in the embodiment 0 /Fe 0 The magnetic susceptibility of the composite porous material is 5268 multiplied by 10 -7 m 3 Kg, nano Cu 0 /Fe 0 The specific surface area of the composite porous material is 93.4m 2 /g。
Example 3
Nano Cu 0 /Fe 0 The water treatment method for dephosphorization of the composite porous material comprises the following steps:
s1, preparing phosphorus-containing sewage: the phosphorus in the phosphorus-containing sewage is mainly orthophosphate (PO 4 3- ) The form exists, and the phosphorus concentration in the phosphorus-containing sewage is 10mg/L.
S2, nano Cu in example 1 0 /Fe 0 The composite porous material is filled into an experimental column, wherein the size of the experimental column is as follows: diameter 20mm, height 70mm, nano Cu 0 /Fe 0 The effective height of the composite porous material is 50mm.
S3, introducing the phosphorus-containing sewage into an experimental column, running for 1h at the hydraulic retention time, and measuring the phosphorus concentration in the water; the determination shows that the phosphorus concentration of the effluent is 0.005mg/L, the phosphorus removal rate is about 100%, and the effluent can reach the discharge standard of surface IV water.
Example 4
Nano Cu 0 /Fe 0 The water treatment method for removing phosphorus from the phosphorus-rich river water by using the composite porous material comprises the following steps:
is to use nano Cu in example 1 0 /Fe 0 The composite porous material is filled in a permeable net cage, and the net cage stacks form a permeable dam, so that phosphorus-rich river water permeates and flows through nano Cu 0 /Fe 0 The composite porous material has phosphorus concentration of 5mg/L in the phosphorus-rich river water, and operates with hydraulic retention time of 2h and is used for nano Cu 0 /Fe 0 The composite porous material can remove phosphorus in the phosphorus-rich river water by chemical precipitation, and the phosphorus concentration in the water is measured. The determination shows that the phosphorus concentration of the effluent is 0.006mg/L, the phosphorus removal rate is about 100%, and the effluent can reach the surface IV waterEmission standards.
Example 5
Nano Cu 0 /Fe 0 The water treatment method for synchronously removing and recycling phosphorus from domestic sewage by using the composite porous material comprises the following steps:
is to adopt nano Cu in the embodiment 2 0 /Fe 0 Filling the composite porous material into a filter tank, allowing the secondary biochemical treated domestic sewage to permeate through the filter tank, wherein the phosphorus concentration is 2mg/L, and the composite porous material operates with a hydraulic retention time of 3h and is used for nano Cu 0 /Fe 0 The composite porous material can synchronously remove and recycle phosphorus under the action of the composite porous material, and the phosphorus concentration in the effluent is measured. The phosphorus concentration of the effluent is measured to be 0.008mg/L, the phosphorus removal rate is about 100%, and the effluent can reach the discharge standard of surface IV water.
Example 6
Nano Cu 0 /Fe 0 The water treatment method for synchronously removing and recycling phosphorus by using the composite porous material in the artificial wetland comprises the following steps:
is to adopt nano Cu in the embodiment 2 0 /Fe 0 Filling the composite porous material into the constructed wetland as a matrix of the constructed wetland, and introducing the phosphorus-rich wastewater into the constructed wetland, wherein the phosphorus concentration is 8mg/L, and the composite porous material operates with a hydraulic retention time of 10h and is used for nano Cu 0 /Fe 0 The composite porous material can synchronously remove and recycle phosphorus under the action of the composite porous material, and the phosphorus concentration in the effluent is measured. According to measurement, the phosphorus concentration of the effluent is 0.004mg/L, the phosphorus removal rate is about 100%, and the effluent can reach the discharge standard of surface IV water.
The above examples are described for adsorbing saturated phosphorus-rich nano Cu 0 /Fe 0 The composite porous material can be used as nutrient soil for soilless culture, promotes plant growth, and realizes synchronous removal and recovery of phosphorus in water.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. Nanometer Cu 0 /Fe 0 The water treatment method for dephosphorizing composite porous material is characterized by comprising the steps of mixing nano Cu 0 /Fe 0 Adding the composite porous material into the phosphorus-containing sewage to remove phosphorus in the phosphorus-containing sewage; wherein, nanometer Cu 0 /Fe 0 The composite porous material is obtained by mixing natural iron ore mineral powder and natural copper carbonate mineral powder and roasting in an oxygen-free atmosphere; the roasting temperature is 800-1200 ℃ and the roasting time is 1-2h;
the mass ratio of the natural iron ore mineral powder to the natural copper carbonate mineral powder is 1-3:1, a step of;
the grain diameter of the natural iron ore mineral powder is less than or equal to 0.1mm, wherein the content of Fe is 30-55%; the grain diameter of the natural copper carbonate mineral powder is less than or equal to 0.1mm, wherein the Cu content is 40-70%.
2. The nano Cu of claim 1 0 /Fe 0 The water treatment method for removing phosphorus by the composite porous material is characterized in that the phosphorus-containing sewage comprises phosphorus-rich river water, phosphorus-rich landscape water, domestic sewage and polluted underground water.
3. The nano Cu of claim 2 0 /Fe 0 The water treatment method for dephosphorization of the composite porous material is characterized in that when the method is used for treating phosphorus-rich river water, nano Cu is adopted 0 /Fe 0 The composite porous material is filled in a deep water pool in front of a drop dam of a river channel or in a permeable net cage, and the net cage stacks form a permeable dam, so that phosphorus-rich river water permeates and flows through nano Cu 0 /Fe 0 A composite porous material.
4. The nano Cu of claim 2 0 /Fe 0 The water treatment method for dephosphorizing the composite porous material is characterized in that when the method is used for treating the phosphorus-rich landscape water body, nano Cu is adopted 0 /Fe 0 Filling the composite porous material into a filter tank, and pumping water of the phosphorus-rich landscape water body to make the water permeate flowAnd a filtering tank.
5. The nano Cu of claim 2 0 /Fe 0 The water treatment method for dephosphorizing composite porous material is characterized by that when it is used for treating domestic sewage, nano Cu is used 0 /Fe 0 Filling the composite porous material into a filter tank, and allowing the domestic sewage after the secondary biochemical treatment to permeate through the filter tank;
or nano Cu 0 /Fe 0 Filling the composite porous material into a biological aerated filter, then conveying the domestic sewage after suspended matters are removed by precipitation into the biological aerated filter by a pump, and aerating the bottom, wherein the air-water ratio is 1:1-2;
or nano Cu 0 /Fe 0 Filling the composite porous material into an anaerobic biological filter, then conveying the domestic sewage after removing suspended matters by precipitation into the anaerobic biological filter by a pump, and continuously feeding water for 0.5-2h by adopting sequencing batch operation;
or nano Cu 0 /Fe 0 Filling the composite porous material into the constructed wetland to be used as a matrix of the constructed wetland, and then conveying the domestic sewage after suspended matters are removed by precipitation into the constructed wetland by a pump, wherein continuous operation is adopted;
or nano Cu 0 /Fe 0 The composite porous material is used as a matrix of a sponge city, and the domestic sewage after suspended matters are removed by precipitation is conveyed into the constructed wetland by a pump, so that continuous operation is adopted.
6. The nano Cu of claim 2 0 /Fe 0 A water treatment method for removing phosphorus by composite porous material is characterized in that when used for treating polluted groundwater, grooves are dug in a polluted aquifer which is vertical to the flowing direction of the groundwater, and nano Cu is used for treating the polluted groundwater 0 /Fe 0 The composite porous material is filled into the excavated grooves to form the permeable walls through which water flows.
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| CN105776506A (en) * | 2016-05-13 | 2016-07-20 | 合肥工业大学 | Fe/C composite porous structure material as well as preparation method and application thereof |
| CN111151226A (en) * | 2020-01-10 | 2020-05-15 | 湘潭大学 | Preparation method and application of copper-iron-carbon nanogel pellets |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105776506A (en) * | 2016-05-13 | 2016-07-20 | 合肥工业大学 | Fe/C composite porous structure material as well as preparation method and application thereof |
| CN111151226A (en) * | 2020-01-10 | 2020-05-15 | 湘潭大学 | Preparation method and application of copper-iron-carbon nanogel pellets |
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| Title |
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| nvestigating the design parameters for a permeable reactive barrier consisting of nanoscale zero-valent iron and bimetallic iron/;Osama Eljamal et al;《Journal Of Molecular Liquids》;20191119;第299卷;摘要、第2.1-4节 * |
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