CN116395728A - Preparation method of fly ash-based hydrotalcite-like compound, and product and application thereof - Google Patents
Preparation method of fly ash-based hydrotalcite-like compound, and product and application thereof Download PDFInfo
- Publication number
- CN116395728A CN116395728A CN202310296901.9A CN202310296901A CN116395728A CN 116395728 A CN116395728 A CN 116395728A CN 202310296901 A CN202310296901 A CN 202310296901A CN 116395728 A CN116395728 A CN 116395728A
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- Prior art keywords
- fly ash
- adsorption
- based hydrotalcite
- compound
- water
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Links
- 239000010881 fly ash Substances 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000011282 treatment Methods 0.000 claims abstract description 35
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims abstract description 15
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 13
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 13
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000012982 microporous membrane Substances 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 110
- 238000000034 method Methods 0.000 claims description 32
- 235000014676 Phragmites communis Nutrition 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 10
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 5
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
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- 239000010865 sewage Substances 0.000 abstract description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract 2
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
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- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 4
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- 241000196324 Embryophyta Species 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- 241000588769 Proteus <enterobacteria> Species 0.000 description 2
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- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
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- 238000012851 eutrophication Methods 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- -1 magnesium aluminum iron Chemical compound 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010018901 Haemoglobinaemia Diseases 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910013504 M-O-M Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 230000001546 nitrifying effect Effects 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 235000010333 potassium nitrate Nutrition 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method of fly ash-based hydrotalcite-like compound, a product and application thereof, and belongs to the technical field of nitrogen-containing sewage treatment. The invention takes fly ash and magnesium chloride as raw materials, adds into hydrochloric acid, heats in water bath, adopts microporous membrane for filtration, adjusts pH value to 11.5, carries out ageing treatment and hydrothermal treatment, centrifugates, washes and dries to obtain the fly ash-based hydrotalcite. The fly ash-based hydrotalcite-like compound is used for removing nitrate nitrogen in water, and the removal rate can reach more than 95%.
Description
Technical Field
The invention belongs to the technical field of nitrogen-containing sewage treatment, and particularly relates to a preparation method of fly ash-based hydrotalcite-like compound, a product and application thereof.
Background
Nitrogen is one of two major limiting elements that cause eutrophication of water bodies. High concentrations of nitrate nitrogen in drinking water also increase the risk of disease and health effects such as hemoglobinemia, diabetes, spontaneous abortion, thyroid diseases and gastric cancer. The sources of nitrogen in the water body mainly include nitrogen fertilizer, animal manure, emission of nitrogen in tail water (secondary effluent) of a sewage treatment plant and the like, wherein the emission of nitrogen in the secondary effluent causes serious eutrophication of surrounding water body. At present, most urban sewage treatment plants in China adopt a secondary treatment process, and effluent usually executes a primary A standard in pollutant emission Standard of urban sewage treatment plants (GB 18918-2002). After the town sewage reaches the discharge standard after being treated, the TN content (15 mg/L) in the effluent is far higher than the V-type water standard (2.0 mg/L) of the surface water environment quality standard (GB 3838-2002). In addition, the secondary effluent is directly discharged into a surface water system, and a certain pollution load impact is caused on the discharged surface water, so that the water body is eutrophicated, the safety of drinking water is threatened, and the like. Therefore, urban sewage treatment needs to achieve the same level of drainage (the same as the environmental quality index of the discharged water), and the secondary effluent is required to be subjected to advanced treatment at the moment. According to the current situation, the secondary effluent has the common conditions of low C/N ratio, low organic matter concentration and high TN content, and the main form of nitrogen in TN is NO 3 - N (about 90%), thus for NO in the second stage 3 - The further removal of N has become an important issue.
Fly ash is a dust-like particle trapped in the flue gas of a combustion furnace and is typical in the worldIs one of the industrial solid wastes. At present, various industries have tried the resource utilization of fly ash, for example in the fields of construction, agriculture, mining and environmental protection, as cement and concrete additives, fertilizers or soil conditioners, mine backfill and water or waste gas treatment materials, respectively. In addition, there are various high value-added applications such as extraction of alumina, rare metals, cenospheres or magnetic beads, and the manufacture of ceramic membranes, molecular sieves or catalyst supports. Fly ash generally contains 20-35% Al 2 O 3 Also small amounts of CaO and Fe 2 O 3 The Al source, ca source and Fe source can be utilized to prepare hydrotalcite-like compound, so that the resource utilization way of the fly ash is expanded, the added value of the fly ash product is improved, and an inexpensive raw material is also found for the artificial preparation of the hydrotalcite-like compound. Researchers generally adopt an acid leaching-coprecipitation method to synthesize hydrotalcite from fly ash, and a large amount of acid wastewater is generated after aluminum is extracted by the method, and the method has complex steps and high synthesis cost; after the reaction is completed, a large amount of clean water is needed for washing the hydrotalcite and the mother solution, and alkaline pollution is brought to the environment. Therefore, a simple and low-pollution method is needed for synthesizing hydrotalcite and has good effect of adsorbing nitrate nitrogen.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of fly ash-based hydrotalcite-like compound, a product and application thereof. The hydrotalcite-like compound is prepared by taking the fly ash as a raw material through a hydrothermal synthesis method, and is taken as a filler, so that the effect and the mechanism of the constructed wetland system for removing nitrogen in secondary effluent are researched, and scientific guidance is provided for constructing and operating the constructed wetland for efficiently removing nitrogen in secondary water.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the fly ash-based hydrotalcite-like compound comprises the following steps: adding fly ash and magnesium chloride hexahydrate as raw materials into hydrochloric acid, heating in a water bath, filtering by adopting a microporous membrane, adjusting the pH value to 11.5, performing aging treatment and hydrothermal treatment, centrifugally separating a solid part, washing with deionized water for three times, and drying at 70 ℃ for 12 hours to obtain the fly ash-based hydrotalcite-like compound; the mass ratio of the fly ash to the magnesium chloride hexahydrate is 5: 5.684.
Further, the water bath heating is to heat in a water bath at 100 ℃ for 2 hours.
Further, the aging treatment is to age the alkaline solution for 30min while stirring at 65 ℃.
Further, the hydrothermal treatment is carried out in an environment of 70 ℃ for 12 hours.
The invention also provides the fly ash-based hydrotalcite-like compound prepared by the preparation method.
The invention also provides application of the fly ash-based hydrotalcite-like compound in adsorbing nitrate nitrogen.
The invention also provides application of the fly ash-based hydrotalcite-like compound as an artificial wetland filler, wherein the artificial wetland filler also comprises iron powder and activated carbon powder.
Further, the mass ratio of the fly ash-based hydrotalcite-like compound, the iron powder and the activated carbon powder is 2:2:1.
Further, when the fly ash-based hydrotalcite-like compound is used for removing nitrate nitrogen in the constructed wetland filler, reed is planted on the wetland. In the setting of the artificial wetland, coarse quartz sand-fine quartz sand-fly ash-based hydrotalcite-like compound, iron powder and active carbon powder mixture-fine quartz sand are sequentially arranged from bottom to top, and reed is planted at the same time.
Compared with the prior art, the invention has the following advantages and technical effects:
the method for preparing hydrotalcite-like compound by using the fly ash as the raw material is simple, and the obtained hydrotalcite-like compound has good adsorption performance, higher removal rate of nitrate nitrogen, high buffer capacity and wide application prospect in wastewater purification.
The prepared hydrotalcite-like compound, iron powder and activated carbon powder are used as the constructed wetland filler, and the operation of planting reed is combined, so that the effect of removing more than 95% of nitrate nitrogen is achieved, and the reed, microorganisms, hydrotalcite-like compound and iron carbon have good coordination effect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is an XRD spectrum for HT;
FIG. 2 is a chart of HT adsorption of NO 3 - FTIR spectra before and after N;
fig. 3 is an SEM image of HT; a. b is a scanning electron microscope characterization map of HT; c. d is HT adsorption of NO 3 - -scanning electron microscope characterization after N;
FIG. 4 is a chart of HT adsorption of NO 3 - -EDS spectra before and after N; a is an EDS energy spectrum of HT; b is HT adsorption of NO 3 - -EDS profile after N;
FIG. 5 is a graph showing the effect of HT adsorption conditions on adsorption performance; a is the rotation speed to HT adsorption NO 3 - -influence of N; b is solid-liquid comparison HT adsorption NO 3 - -influence of N; c is pH to HT adsorption of NO 3 - -influence of N;
FIG. 6 is the adsorption time versus HT adsorption of NO 3 - -influence of N;
FIG. 7 is HT vs. NO 3 - -a kinetic model of the adsorption mechanism of N; a is HT adsorption of NO 3 - -a quasi-first order kinetic model of N; b is a quasi-second order dynamics model; c is an intra-particle diffusion kinetics model;
FIG. 8 is HT vs. NO 3 - -an adsorption isotherm model of N; a is HT adsorption of NO 3 - -Freundlich adsorption isothermal model of N; b is a Langmuir adsorption isothermal model;
FIG. 9 is a chart of HT adsorption of NO 3 - -an adsorption thermodynamic diagram of N;
FIG. 10 is a schematic diagram of a vertical flow constructed wetland system;
FIG. 11 shows the variation of COD average removal rate of each system at different HRT;
FIG. 12 is a schematic diagram of the NH systems at different HRT 4 + -a change in the N average removal rate;
FIG. 13 shows the NO of the systems at different HRT 3 - Variation of the average removal rate of NPerforming chemical treatment;
FIG. 14 is a graph showing the variation of TN average removal rate for each system at different HRTs;
FIG. 15 is a graph showing the variation of average removal rate for each system TP at different HRTs;
FIG. 16 shows the variation of COD average removal rate of each system at different HRT;
FIG. 17 is a diagram of the NH systems at different HRT 4 + -a change in the N average removal rate;
FIG. 18 shows the NO of the systems at different HRT 3 - -a change in the N average removal rate;
FIG. 19 is a graph showing the variation of TN average removal rate for each system at different HRT;
fig. 20 shows the variation of average removal rate of each system TP at different HRTs.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "room temperature" and "normal temperature" in the present invention are all calculated at 25.+ -. 2 ℃ unless otherwise specified.
1. Method for removing NO in water by using fly ash-based hydrotalcite-like compound 3 - Investigation of-N
1.1 materials and methods
1.1.1 Experimental raw materials
The main components obtained by analysis of the dried fly ash by an X-ray diffractometer are shown in Table 1. Grinding a Fly Ash (FA) sample, sieving with a 100-mesh sieve, drying at 105 ℃ to constant weight, naturally cooling in a dryer, and filling into a sealing bag for standby.
TABLE 1 essential components (wt%) of fly ash
TABLE 2 Main laboratory apparatus
1.1.2 Experimental methods and designs
(1) Hydrotalcite-like synthesis experiment
5g of fly ash and 5.684g of magnesium chloride hexahydrate are added to 100mL of 3mol/L hydrochloric acid, the suspension is filtered using a 0.45 micron pore membrane in a water bath at 100 ℃ for 2 hours; gradually adding 2mol/L sodium hydroxide until the pH value reaches 11.5, and aging the alkaline solution for 30min while stirring at 65 ℃; carrying out hydrothermal treatment for 12 hours in a reaction kettle in a hot air oven at 70 ℃; the solid fraction was separated by centrifugation, washed three times with deionized water and dried at 70 ℃ for 12h to give hydrotalcite-like HT.
(2) Material characterization method
Analysis of the hydrotalcite-like crystalline phase by X-ray diffraction (XRD); determining the change condition of the functional groups on the surface of the material before and after adsorption by using Fourier transform infrared (FT-IR); the hydrotalcite-like surface morphology and surface element composition were determined by Scanning Electron Microscopy (SEM) in combination with X-ray spectroscopy (EDX) after metal spraying.
(3) Batch adsorption experiments
The adsorption experiment of HT is carried out by a batch experiment mode, and NO is prepared by potassium nitrate 3 - Ion stock solution with N concentration of 1g/L, NO with other concentration used in experiment 3 - The N solutions were all diluted from the stock solution. The whole adsorption experiment is carried out in a constant temperature vibrating box, supernatant is separated by using 0.45 mu m filter paper and then diluted to be in the measuring range of an ultraviolet spectrophotometer for concentration measurement, and all experimental treatments are repeated three times.
Determination of experimental conditions (rotation speed, solid-to-liquid ratio, pH): experiments were performed using a one-factor method in which the rotational speeds were 50rpm, 100rpm, 150rpm, 200rpm and 250rpm; the addition amounts are 1g/L, 1.5g/L, 2g/L, 4g/L and 6g/L respectively; the pH values are 3, 5, 7, 9 and 11 respectively; other experimental factors were set as: NO (NO) 3 - The initial concentration of the N solution was 15mg/L, the reaction time was 20min and the temperature was 25 ℃. NO (NO) 3 - The calculation method of the N removal rate and the adsorption amount are respectively as follows:
wherein: r is the removal rate (%), C 0 Is NO 3 - Initial concentration of N solution (mg/L), C t For time t NO 3 - Concentration of-N solution (mg/L), q t The adsorption capacity at time t (mg N/g), V is the adsorption solution volume (L), and M is the HT mass (g).
Adsorption kinetics: accurately weigh 0.04g HT into 150mL Erlenmeyer flask containing 20mL solution, NO 3 - The N concentration was 15mg/L, the pH was 9.0, the temperature was 25℃and the rotational speed was 200rpm. Simultaneously preparing a plurality of repeated samples, respectively taking 3 repeated samples from 5, 10, 15, 20, 25 and 30min from the beginning of the adsorption reaction, immediately filtering out the solution and measuring the concentration.
Adsorption isotherm and adsorption thermodynamics: accurately weigh 0.04g HT into 150mL Erlenmeyer flask containing 20mL solution, NO 3 - The N concentration is 10-120mg/L, the temperature is 18, 25 and 35 ℃, the pH value is 9.0, the rotating speed is 200rpm, and the adsorption time is 20min.
1.2 results and discussion
1.2.1HT characterization and analysis of materials
(1)XRD
The XRD patterns of HT are shown in FIG. 1. Diffraction peaks appearing at 2θ= 11.001 °, 22.091 ° and 34.143 ° correspond to (003), (006) and (012) crystal planes, respectively, indicating that a layered double hydroxide structure is formed. The low 2 theta value has high intensity, symmetry and small width peaks, which indicates that the synthesized material has the characteristic of lamellar material with high crystallinity. The peak at 2θ= 59.985 ° is a metal oxide lattice, further illustrating that the prepared sample is a high crystallinity magnesium aluminum iron hydrotalcite-like compound. The peak observed at 2θ= 29.405 ° is CaCO 3 I.e., calcite, which is a by-product formed during the synthesis of the material.
(2)FTIR
HT adsorption of NO 3 - The FTIR spectra before and after N are shown in FIG. 2. First, the wave number is 3448cm -1 And 3464cm -1 A characteristic peak was observed, which was attributed to the stretching vibration of hydroxyl groups (O-H), which was formed by overlapping the stretching vibration of the laminate hydroxyl groups of LDH and interlayer water molecules. Next, 1629cm -1 And 1637cm -1 Surface water and interlaminar layer with peak LDHBending vibration peaks of water molecules. Indicating HT interlayer CO 3 2- The peak may be present at 1424cm -1 It was observed that it was CO 3 2- Is an antisymmetric stretching vibration peak of (a). At 1053cm -1 、1046cm -1 、590cm -1 And 577cm -1 The nearby energy bands coincide with lattice vibrations: such as M-O, M-OH and M-O-M groups in HT (where m=mg, al and Fe). Briefly, the spectrum shows MgAlFe-CO 3 Successful synthesis of LDH. HT adsorption of NO 3 - 1385cm in the N-post-map -1 The strong band at n=o tensile vibration, indicating that nitrate ions have been intercalated into the middle layer of HT. CO-free 3 2- Peaks present, indicating that HT adsorbs NO 3 - One of the mechanisms of-N is ion exchange.
(3)SEM-EDS
SEM image (FIG. 3) shows that NO is adsorbed 3 - There is a clear difference in the morphology of HT before and after N. The HT before adsorption has a polygonal structure and irregular edges, and the surface of the HT is smooth and flat and is lamellar (a in fig. 3). Adsorption of NO 3 - After N (b in FIG. 3), HT lamellar morphology remains unchanged, the surface becomes uneven, indicating NO 3 - N has adsorbed onto the HT surface.
HT adsorption of NO 3 - The EDS energy spectra before and after-N are shown in FIG. 4. Adsorption of NO 3 - After N, the intensities of the C and Cl peaks in HT, representing the C and Cl contents respectively, decrease, and the N peak representing the N content appears, while the C content decreases from 43.46% to 24.90%, the Cl content decreases from 2.06% to 1.12%, and the N content increases from 0% to 2.47%, indicating NO 3 - And Cl - 、CO 3 2- Ion exchange occurs therebetween.
1.2.2HT study on the adsorption of nitrate Nitrogen
(1) Determination of HT adsorption conditions (rotation speed, addition amount, pH)
Determining the rotating speed: the experimental results are shown in FIG. 5, a, where NO is found at 200rpm 3 - The removal rate of N is the highest and is 70.84%. NO during increase of rotation speed from 50rpm to 200rpm 3 - The removal rate of N increases gradually, because the oscillator speed increases, improving HT and NO 3 - The contact frequency of N and the dispersion of HT in the solution are improved, thus facilitating the adsorption process. When the rotation speed exceeds 200rpm, the rotation speed is increased, and most of the adsorbent rotates at the center of the conical flask to form a vortex-shaped adsorption column, so that the contact opportunity of the liquid on the side wall of the conical flask with HT is reduced, and the removal rate is reduced. In addition, when adsorption reaches a certain degree, dynamic balance of adsorption and desorption exists, and the too high rotating speed can increase the desorption speed, so that the adsorption efficiency of the whole system is reduced. The test speed was set at 200rpm.
Determining the addition amount: as shown in b of FIG. 5, the experimental results show that NO 3 - The removal rate of N rises significantly and then slowly. When the dosage is 0.16g, NO 3 - The removal rate of N reaches 90.79 percent. This is because HT surfaces are heterogeneous and their removal rate is closely related to their surface active sites. With the increase of the adding amount, the active point positions are increased, the surface adsorption is saturated rapidly, and NO 3 - -a significant increase in N removal rate. After the addition amount is increased to a certain value, HT is further added, and the effective surface area of the adsorbent is not obviously increased due to the agglomeration of the nano particles, namely the active point is not obviously increased, so that the removal rate is not obviously improved. And combining with economic benefits, the HT dosage is selected to be 0.04g in the subsequent experiment.
Determination of pH: the experimental results are shown in fig. 5c, where the pH is in the range of 3-9, and the adsorption effect increases slowly with increasing pH, probably because hydrotalcite-like compounds are partially dissolved in an acidic environment. When the pH is more than 9, the adsorption effect is slowly decreased, probably due to OH in the solution - Increased concentration, increased competitive adsorption with nitrate, resulting in NO 3 - -a decrease in the N removal rate. Moreover, HT shows a good adsorption effect on NO when the pH fluctuates between 3 and 11 3 - The removal rate of N reaches above 63%, which shows that HT vs. NO in a certain pH range 3 - The influence of the adsorption capacity of N is not very pronounced, the range of application is very largeAnd (3) wide range. Because of NO 3 - The removal rate of N is highest at a pH of 9, and the initial pH of the solution is chosen to be 9 in the subsequent experiments.
In addition, HT adsorbs NO 3 - After N, the pH rises, possibly due to OH in the hydrotalcite - Is released. In addition to an initial pH of 11, the final pH was between 6.3 and 7.0, indicating that HT had a higher buffer capacity.
(2) Adsorption kinetics
Adsorption time to HT adsorption of NO 3 - The effect of N is shown in FIG. 6. The HT removal rate increases significantly within 10min of adsorption time, after which the rate of change of removal rate slows down and adsorption equilibrium is gradually reached at 20min. Therefore, the subsequent operation of this experiment was performed for 20min as adsorption time.
To intensively study HT versus NO 3 - The adsorption mechanism of N adopts 3 different kinetic models of a quasi-first-order kinetic model, a quasi-second-order kinetic model and an intra-particle diffusion kinetic model to fit experimental data, and the experimental data are respectively represented by the following equations:
ln(q e -q t )＝lnq e -k 1 t (3)
q t ＝k 3 t 1/2 +C (5)
wherein: t is adsorption time (min), q e Is the adsorption capacity at equilibrium (mgNg -1 )，k 1 Adsorption rate constant (min) as a pseudo first order kinetic equation -1 )，k 2 Adsorption rate constant (gmg) as a pseudo-second order kinetic equation -1 min -1 )，k 3 Is the intraparticle diffusion constant (mg g) -1 min -1/2 ) C is a constant that characterizes the diffusion of the solute into the liquid phase.
TABLE 3 HT adsorption of NO 3 - -N kinetic model fitting parameters
As can be seen from the intra-particle diffusion kinetics model (c in fig. 7), the adsorption process can be divided into two phases: a fast adsorption stage and a slow adsorption stage. The rapid adsorption phase is due to NO 3 - The transfer of N from the solution to the HT outer surface, representing HT and NO 3 - Interaction between-N, the second stage is due to NO 3 - N gradually penetrates into the pores of HT, and intra-granular diffusion is slowed by the reduced concentration. It can also be seen that the value of the constant C is not 0 (table 3), indicating that intra-particle diffusion is not the only limiting step. Other control steps such as chemisorption, boundary layer effects, etc. may be present during the adsorption process. Comparing the correlation coefficients of 3 kinetic models (a in FIG. 7, b in FIG. 7, c in FIG. 7), HT adsorbs NO 3 - The process N is more in line with a pseudo-secondary reaction dynamics model, and the linear correlation coefficient reaches 0.997. Description of chemisorption is NO 3 - -a rate limiting step of N adsorption. The theoretical equilibrium adsorption quantity calculated by the quasi-second-stage reaction kinetic equation is 5.705mg/g, which basically coincides with the experimental value of 5.60 mg/g.
(3) Adsorption isotherm
Adsorption isotherms and simulation results provide important information for analyzing the interaction mechanism between adsorbents and the maximum adsorption capacity of the adsorbents. The equations for the Langmuir and Freundlich models are as follows:
wherein: q max Is the maximum adsorption quantity (mg N g) -1 )，k L Is Ladsorption energy constant of angmuir model (Lmg) -1 )，k f Adsorption quantity constant for Freundlich model ((L mg) -1 ) 1/n mg g -1 ) N is the adsorption strength constant.
In the Langmuir isothermal adsorption model, HT adsorption of NO can be analyzed with the following parameters 3 - Effect of N:
wherein: RL is the balance parameter.
The isothermal curves obtained from these models are shown in fig. 8, and the parameters derived from each model are shown in table 4. R of Langmuir model compared to Freundlich model at different adsorption temperatures 2 The correlation coefficient is closer to 1, indicating NO 3 - N is homogeneous on the adsorbent surface, the adsorption may be monolayer adsorption. HT vs. NO at 25 DEG C 3 - The maximum adsorption amount of-N was 11.126mgN/g. R is R L <1 indicates good adsorption. Dimensionless constant R calculated by equation (8) L 0.43, 0.49 and 0.57, respectively, indicating that HT pair adsorbs NO 3 - The N solution has good adsorption effect.
TABLE 4 HT adsorption of NO 3 - Adsorption isothermal model fitting parameters of-N
(4) Adsorption thermodynamics
As can be seen from the parameters of Table 4, HT removes NO when the experimental temperature is increased from 291.15K to 308.15K 3 - Q of-N max Gradually increasing. By thermodynamic parameter Gibbs free energy (. DELTA.G o ) The entropy (Δs°) and the enthalpy (Δh°) describe this process. These parameters can be found by the following formula:
ΔG o ＝-RTlnk d (9)
wherein: k (k) d For adsorption distribution coefficient ΔG o Is Gibbs free energy (kJmol) -1 ) ΔH° is the change in adsorption enthalpy (kJmol) -1 ) ΔS° is the adsorption entropy change (Jmol) -1 K -1 ) R is molar gas constant, 8.314 (J/mol) -1 K -1 ) T is the thermodynamic temperature (K).
Wherein, when the adsorption data accords with the Langmuir isotherm model, the distribution ratio can be defined by k d ＝106k L And (5) calculating. As shown in Table 5, ΔG° (-11.970 to-12.036 kJmol) -1 ) Negative value, indicating NO 3 - The adsorption of N onto HT occurs spontaneously. The absolute value of Δg ° gradually increases with increasing temperature, indicating that adsorption reaction proceeds favorably at high temperature. ΔH° (-10.772 kJmol) -1 ) Negative value, indicating NO 3 - The adsorption of N on HT is an exothermic process. ΔS° (4.156 Jmol) -1 K -1 ) Is positive, and shows that the adsorption experiment is a process of increasing the degree of freedom at the solid-liquid interface (FIG. 9 shows that HT adsorbs NO 3 - -adsorption thermodynamic diagram of N).
TABLE 5 HT adsorption of NO 3 - Thermodynamic parameters of-N
1.3 knots
The invention prepares hydrotalcite-like HT by using fly ash through hydrothermal synthesis method, and characterizes the HT, and researches NO by the HT 3 - Adsorption properties of N. The results show that HT vs. NO at different initial pH conditions 3 - The N removal rate is kept at a high level and has a high buffer capacity (final pH is kept between 6 and 7). The kinetic data is described by a quasi-second-order kinetic model, which shows that the reaction speed limiting step is chemical adsorption. The experimental data fit well to the Langmuir model, with a maximum adsorption of 11.126mgN/g at 25 ℃. Heat of the bodyThe mechanical parameters indicate that the adsorption process is spontaneous, exothermic. HT for removing NO from water 3 - The main adsorption mechanisms of N are electrostatic attraction and ion exchange. In general, HT has good adsorption performance and has wide application prospect in wastewater purification.
2. Removal effect of hydrotalcite-like coupling iron-carbon micro-electrolysis constructed wetland on secondary effluent
2.1 materials and methods
2.1.1 the filler used in the experiment is hydrotalcite-like compound prepared in the prior art, the sample is pretreated by grinding and sieving with a 100-mesh sieve, and the sample is dried to constant weight at 105 ℃, then naturally cooled in a dryer and filled into a sealing bag for standby. 2.1.2 constructed wetland Experimental design
The constructed wetland device (shown in figure 10) is formed by bonding a PVC pipe with the height of 50cm and the inner diameter of 10cm with a cap, wherein the total effective volume is 3.9L, and the effective water volume is 1L. Coarse quartz sand (particle size about 9-12 mm) with the height of 5cm is paved at the bottom of each reactor, a water inlet is prevented from being blocked by a matrix, uniform water distribution is facilitated, fine quartz sand (particle size about 4-8 mm) with the main body height of 31cm is arranged at the upper part of the coarse quartz sand, a mixture of hydrotalcite-like compound, iron powder (Mitsui factory) and wood powder activated carbon (Yu and environment-friendly material factory) with the mass ratio of 2:2:1 is paved in the middle of the fine quartz sand, and 2 reed plants are planted above the quartz sand. Water inlets and outlets were arranged at 3cm and 45 cm.
Common reed is selected from wetland plants, tap water is used for cleaning the reed root coefficient, reed with consistent growth vigor is taken and transplanted into a wetland device, and 2 reed plants are planted in each device. The test is divided into two groups of non-planted reed and planted reed, and each group has 4 treatments. The reed group is not planted: the substrate is quartz sand (CK 1) only, which is control treatment 1; the treatment of adding hydrotalcite-like compound is HT1; the treatment of adding the mixture of iron powder and activated carbon powder is Fe-C1; the treatment of adding the mixture of hydrotalcite-like compound, iron powder and activated carbon powder is HT-Fe-C1. Planting reed groups: the matrix is only quartz sand (CK 2), the control treatment 2 is added with hydrotalcite-like compound, and the treatment is HT2; the treatment of adding the mixture of iron powder and activated carbon powder is Fe-C2; the treatment of adding the mixture of hydrotalcite-like compound, iron powder and activated carbon powder is FA-Fe-C2. In reed planting group, hydrotalcite-like compound, iron powder and active carbon powder are paved at the position 20cm away from the bottom of the device, the thickness is 1cm, and the paving positions are all near the root system of reed. Correspondingly, in the group without reed planting, hydrotalcite-like compound, iron powder and active carbon powder are paved at the same position, and the thickness is 1cm. Each wetland system was set up with 3 replicates. And inoculating denitrified sludge of sewage treatment plants of university of Chinese mining into the device, and starting a test after the system is stabilized, namely the removal rate of each pollutant in the effluent is stabilized.
The wetland system adopts an intermittent water inlet mode, the water inlet flow of the wetland system is 8.33mL/min, and the water inlet flow is controlled by a peristaltic pump. The water quality of secondary effluent of sewage treatment plant is simulated by water inflow, which is prepared manually, and nitrate nitrogen (NO 3 - -N), ammonia Nitrogen (NH) 4 + -N), phosphate (PO 4 3- ) Organic matter (COD) Cr Meter) with KNO respectively 3 、NH 4 Cl、KH 2 PO 4 And CH (CH) 3 COONa is prepared, the solvent is deionized water, and the index of the water quality of the system inlet water is shown in Table 8.
Table 8 system inlet water quality
The wetland system operates at a temperature of more than or equal to 25 ℃. During operation of each system, the hydraulic retention time is sequentially 1d, 3d, 5d and 7d, each hydraulic retention time is one operation period, and three periods are sampled continuously under each hydraulic retention time.
2.1.3 method for determining experimental index
The test adopts the national standard method to the water quality index (comprising TN, NO) 3 - -N、NO 2 - -N、TP、COD Cr And pH). The corresponding measurement methods are shown in Table 9.
TABLE 9 Water quality measurement index and method
2.1.4 Experimental data processing method
Experimental data were collated using Microsoft Excel 2019 software; using SPSS26.0 software, performing a differential analysis between wetland systems by using a single-factor analysis of variance method, and considering that the difference between the results is significant at the level p < 0.05; graphics were drawn using Origin2018 software.
2.2 results and discussion
2.2.1 analysis of pollutant removal Effect of Reed-not-planted wetland System under different hydraulic retention times
2.2.1.1 Effect of different hydraulic retention times on dichromate index
The pollution degree of organic matters in the water body can be used as COD Cr Evaluating COD of water inlet and outlet of the constructed wetland system Cr The concentration ranges are shown in Table 10.
TABLE 10 COD of incoming and outgoing water treated differently Cr Concentration range
FIG. 11 is a graph showing the variation of average removal rate of COD of each system at different HRTs, wherein different capital letters indicate the significance of difference (P < 0.05) of average removal rate of the same system at different HRTs; different lower case letters represent the significance of difference (P < 0.05) in average removal rate for each system at the same HRT (other pictures are the same and will not be described in detail later). It was found that as HRT increases, the COD water concentration of each system gradually decreases, and at hrt=1d, 3d and hrt=5d, 7d, the COD removal efficiency of each system is significantly different, because the hydraulic retention time is too short, and the COD in the sewage may not be sufficiently degraded or adsorbed by the system.
In general, the COD water outlet concentration of each system is from small to large, HT-Fe-C1< Fe-C1< HT1< CK1, the COD removal rate of the HT-Fe-C1 and Fe-C1 systems is higher than that of the HT1 and CK1 systems, and the COD water outlet concentration and the COD removal rate of the HT-Fe-C1 and the HT1 systems are obviously different, so that the adsorption capacity of the Fe-C on the COD is higher than that of the HT.
2.2.1.2 different hydraulic residence time pairsNH 4 + Influence of-N
NH during operation of artificial wet land system without reed 4 + Water inlet and outlet concentration of-N and NH at different HRT 4 + The average removal rate of N is shown below, respectively.
TABLE 11 different treatments of influent and effluent NH 4 + -N concentration range
FIG. 12 is a schematic diagram of the NH systems at different HRT 4 + As can be seen from the change plot of the average removal rate of N, the ammonia nitrogen effluent concentration of each system increased slightly as HRT increased, with the highest ammonia nitrogen removal rate at hrt=1d, but overall, there was no significant difference. This is because of NH of the incoming water 4 + The concentration of the-N is lower (about 5 mg/L), the pollution load is smaller, the DO content in the inflow water is higher, the nitrification of nitrifying bacteria in the condition that the HRT is 5d is satisfied, and the NH of the system is ensured 4 + Higher removal rate of N.
In general, the ammonia nitrogen effluent concentration of each system is from small to large Fe-C1<HT1<CK1<FA-Fe-C1, probably because DO drops faster in the FA-Fe-C1 system, NO 3 - Reduction of N to NH 4 + -N, leading to NH 4 + -N concentration higher than other systems. However, in general, the ammonia nitrogen removal rate of each system was not analyzed significantly.
The main species composition ratio of microorganisms of different filler layers of each wetland system at the level of phylum and class can be known that Proteobacteria phylum (Proteobacteria) and Bacteroides phylum (bacterioides) and Chloroflexi (Chloroflexi) are dominant microorganisms in the artificial wetland system; beta-Proteus (Betateobacteria) and alpha-Proteus (alpha-Proteus), gamma-Proteus (Gamma-Proteus), anaerobic rope bacteria (Anaeronolineae) and Sphingobacterium are dominant microorganisms in the constructed wetland system. The Proteus mainly comprises alpha-Proteus, beta-Proteus and gamma-Proteus, and is used in a sewage treatment systemProteus is the most important microorganism, playing an important role in the biodegradation of contaminants, while most denitrifying bacteria belong to Proteus, proving that the system can denitrify by denitrification. The bacteroides can perform anaerobic respiration by using nitrate or nitrite as an electron acceptor under the condition of hypoxia or anaerobic condition to perform autotrophic denitrification. The denitrification by microorganisms is related to the dissolved oxygen concentration, and when the DO content is low, the denitrification is inhibited and promoted. So consider NH 4 + -decrease in N removal rate and NO 3 - The N removal rate increases because DO in the system decreases with increasing HRT. All DO contents in the invention are judged in turn.
2.2.1.3 different hydraulic retention times vs. NO 3 - Influence of-N
NO during operation of artificial wetland system without reed 3 - Water inlet and outlet concentration of-N and NO at different HRT 3 - The average removal rate of N is shown below, respectively.
TABLE 12 different treatments of inlet and outlet water NO 3 - -N concentration range
FIG. 13 shows the NO of the systems at different HRT 3 - Variation of the average removal rate of N, it can be seen from the graph that as HRT increases, NO for each system 3 - -N effluent concentration decreases and then increases, NO at hrt=3d 3 - The highest N removal efficiency. This is probably because when HRT is increased, the DO content in the wetland system gradually decreases due to the progress of the nitrification reaction, so that the denitrification effect is enhanced, and the effect of removing nitrate nitrogen is better. However, as the HRT is increased to 5d and 7d, NO adsorbed by the upper matrix of the system 3 - Gradual resolution of-N, resulting in NO in the system 3 - The N concentration increases and the removal rate decreases.
Overall, NO for each system 3 - The concentration of the discharged water of the-N is from small to large and is HT-Fe-C1<Fe-C1<HT1<NO of CK1, HT-Fe-C1 system 3 - N removal was higher than other systems and there was a significant difference, indicating NO removal 3 - HT and Fe-C act synergistically at N.
2.2.1.4 influence of different hydraulic retention times on TN
The water inlet and outlet concentration of TN during operation of the unsophisticated reed constructed wetland system and the average removal rate of TN at different HRTs are respectively shown as follows.
TABLE 13 TN concentration ranges of different treated inflow and outflow waters
Fig. 14 shows the change of the TN average removal rate of each system at different HRTs, and it can be seen that the TN removal efficiency is highest when hrt=3d, when the TN outlet water concentration of each system decreases and then increases with increasing HRT. This is probably because when HRT is increased, the DO content in the wetland system gradually decreases due to the progress of the nitrification reaction, so that the denitrification effect is enhanced, the effect of removing nitrate nitrogen is better, and the TN content in the system gradually decreases. However, as the HRT is increased to 5d and 7d, nitrogen contaminants adsorbed by the matrix at the upper part of the system are gradually resolved, and due to the longer HRT, denitrification is limited due to insufficient carbon source in the system, and nitrite nitrogen in the system accumulates, the two reasons result in higher TN concentration of the effluent of the system, and TN removal rate of each system is reduced.
In general, TN effluent concentration of each system is from small to large, HT-Fe-C1< Fe-C1< HT1< CK1, TN removal rate of HT-Fe-C1 system is higher than other systems, and significant difference exists, which indicates that HT and Fe-C have synergistic effect when TN is removed.
2.2.1.5 Effect of different hydraulic retention times on TP
The water inlet and outlet concentrations of TP during operation of the unsophisticated reed constructed wetland system are shown below.
TABLE 14 TP concentration ranges for different treatment of incoming and outgoing Water
Fig. 15 shows the variation of the average removal rate of TP for each system at different HRT, and it can be seen that as HRT increases, the total phosphorus water concentration of each system gradually increases, and the TP removal efficiency is highest at hrt=1d. This is because when the pH is <8, physical adsorption is dominant, but desorption is strong, and part of phosphorus on the substrate is desorbed by reverse reaction and released into water again, so that the concentration of TP effluent is increased.
From the system changes, the total phosphorus effluent concentration of each system is from small to large HT1< Fe-C1< HT-Fe-C1< CK1, which indicates that HT has higher adsorption capacity to phosphorus.
2.2.2 analysis of pollutant removal Effect of Reed-planted wetland systems with different hydraulic retention times
2.2.2.1 Effect of different hydraulic retention times on dichromate index
The pollution degree of organic matters in the water body can be used as COD Cr The evaluation is carried out, and the concentration range of the water inlet and outlet CODCr of the constructed wetland system is shown in table 15.
TABLE 15 COD of incoming and outgoing water treated differently Cr Concentration range
Fig. 16 shows the change of average removal rate of COD in each system at different HRT, and it can be seen that as HRT increases, the COD water concentration in each system gradually decreases, and the removal efficiency of COD in each system is significantly different between hrt=1d and hrt=3d, 5d, and 7d, because the hydraulic retention time is too short, and COD in the sewage may not be sufficiently degraded or adsorbed by the system. With the continuous extension of the hydraulic retention time, the increment of the removal rate of COD is reduced and gradually approaches saturation, and the removal rate is not changed obviously any more.
In general, the COD water outlet concentration of each system is from small to large, HT-Fe-C2< Fe-C2< HT2< CK2, the COD removal rate of the HT-Fe-C2 and Fe-C2 systems is higher than that of the HT2 and CK2 systems, and the COD water outlet concentration and the COD removal rate of the HT-Fe-C2 and the HT2 systems are obviously different, so that the adsorption capacity of Fe-C on COD is higher than that of HT.
2.2.2.2 different hydraulic retention times vs. NH 4 + Influence of-N
NH during operation of artificial wet land system without reed 4 + Water inlet and outlet concentration of-N and NH at different HRT 4 + The average removal rate of N is shown below, respectively.
TABLE 16 different treatments of incoming and outgoing NH 4 + -N concentration range
FIG. 17 is a diagram of the NH systems at different HRT 4 + As the HRT increases, the ammonia nitrogen water concentration of each system increases slightly, and the ammonia nitrogen removal rate is highest at hrt=1d, and significantly different from hrt=7d. This is because as HRT increases, DO in the system decreases and NO 3 - Reduction of N to NH 4 + -N, thereby leading to NH 4 + Accumulation of N.
In general, the ammonia nitrogen water outlet concentration of each system is from small to large FA-Fe-C2< HT2< CK2< Fe-C2, but the ammonia nitrogen removal rate of each system has no significant difference, which indicates that the removal effect of low-concentration ammonia nitrogen is less influenced by matrix additives in the wetland in which reed is planted.
2.2.2.3 different hydraulic retention time vs. NO 3 - Influence of-N
NO during operation of artificial wetland system without reed 3 - Water inlet and outlet concentration of-N and NO at different HRT 3 - The average removal rate of N is shown below, respectively.
TABLE 17 different treatments of inlet and outlet water NO 3 - -N concentration range
FIG. 18 shows the NO of the systems at different HRT 3 - Variation of the average removal rate of N, it can be seen from the graph that as HRT increases, NO for each system 3 - When the water concentration of the N outlet drops and then rises, but HRT=3d, 5d and 7d, NO 3 - No significant difference in N removal efficiency. This is probably because, since hrt=3d, other systems than CK2 system are directed to NO 3 - The removal effect of N has reached 97%, so the effect of increasing the HRT is not significant.
Overall, NO for each system 3 - The concentration of the water discharged from the process is from small to large HT-Fe-C2<HT2<Fe-C2<CK2, NO of each system except CK2 system 3 - No significant difference in N removal efficiency. This is probably because the reed root system secretes oxygen, and forms a plurality of aerobic, anoxic and anaerobic microenvironments around the root system in sequence, HT and Fe-C provide carbon sources, and both provide suitable environments for the growth and metabolism of various microorganisms around the root system, resulting in NO 3 - -an increase in the N removal rate.
Effects of different hydraulic retention times of 2.2.2.4 on TN
Inlet and outlet water concentration of TN during operation of unsophisticated reed constructed wetland system and NH under different HRT 4 + The average removal rate of N is shown below, respectively.
Table 18 TN concentration ranges of different treated inflow and outflow waters
Fig. 19 shows the change in the TN average removal rate of each system at different HRTs, and it can be seen from the graph that the TN water concentration of each system decreases and then increases as HRT increases, but the TN removal efficiency does not significantly differ at hrt=3d, 5d, and 7. This is probably because the effect of increasing HRT is not significant because the removal effect of other systems than CK2 system on TN has reached 95% at hrt=3d.
In general, TN effluent concentrations of the respective systems were from small to large HT-Fe-C2< HT2< Fe-C2< CK2, and TN removal efficiencies of the respective systems were not significantly different except for the CK2 system. This is probably because the reed root system secretes oxygen, and a plurality of aerobic, anoxic and anaerobic microenvironments are sequentially formed around the root system, HT and Fe-C provide carbon sources, and both provide suitable environments for the growth and metabolism of various microorganisms near the root system, so that TN removal rate is increased.
Effects of different hydraulic retention times of 2.2.2.5 on TP
The water inlet and outlet concentrations of TP during operation of the unsophisticated reed constructed wetland system are shown below.
TABLE 19 TP concentration ranges for different treatment of incoming and outgoing Water
Fig. 20 shows the variation of the average removal rate of TP for each system at different HRT, and it can be seen from the graph that as HRT increases, the total phosphorus water concentration of each system gradually increases, and the TP removal efficiency is highest at hrt=1d. Hrt=1d and hrt=7d, there is a significant difference between the systems. This is because when the pH is <8, physical adsorption is dominant, but desorption is strong, and part of phosphorus on the substrate is desorbed by reverse reaction and released into water again, so that the concentration of TP effluent is increased.
Overall, the total phosphorus effluent concentration of each system ranges from small to large HT-Fe-C2< HT2< Fe-C2< CK2. The TP removal rate of HT-Fe-C2 is obviously different from the TP removal rates of HT2, fe-C2 and CK2, which is probably because DO in the HT-Fe-C2 system is higher than that in other systems, the metabolic activity of phosphorus bacteria is enhanced, and the phosphorus concentration of the effluent is lower after aerobic phosphorus absorption.
2.3 knots
The invention examines TN and NO in secondary effluent of a sewage treatment plant which is simulated by taking nitrate nitrogen as main pollutant under the condition of different hydraulic retention time by adding hydrotalcite-like coupling iron-carbon micro-electrolysis constructed wetland 3 - -N，NH 4 + -removal effect of N, TP and organic contaminants, test set 4 hydraulic retention times (hrt=1d, 3d, 5d and 7 d). The results show that:
the removal of pollutants by the non-planted reed wetland mainly depends on the adsorption and interception of the matrix and the microbial degradation. TN and NO 3 - The water concentration of-N decreases and then increases with increasing HRT, TN and NO at hrt=3d 3 - -the removal rate of N is highest; NH (NH) 4 + The water outlet concentrations of N and TP gradually increase with the increase of HRT; the effluent concentration of organic contaminants gradually decreases with increasing HRT. At different HRT, each system is used for NH with low concentration 4 + The method has good removal effect on N, and when the wastewater with nitrate nitrogen as main pollutant is treated, the hydrotalcite-like compound and the iron-carbon micro-electrolysis mixture are added to TN and NO 3 - The removal rate of N is higher than that of other systems, and there is a significant difference, indicating that HT and Fe-C act synergistically during denitrification.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (9)
1. The preparation method of the fly ash-based hydrotalcite-like compound is characterized by comprising the following steps of: adding fly ash and magnesium chloride hexahydrate as raw materials into hydrochloric acid, heating in water bath, filtering by adopting a microporous membrane, adjusting the pH value to 11.5, performing ageing treatment and hydrothermal treatment, centrifuging, washing and drying to obtain the fly ash-based hydrotalcite; the mass ratio of the fly ash to the magnesium chloride hexahydrate is 5: 5.684.
2. The method for preparing the fly ash-based hydrotalcite like compound according to claim 1, wherein the water bath heating is performed in a water bath at 100 ℃ for 2 hours.
3. The method for preparing fly ash-based hydrotalcite like compound according to claim 1, wherein the aging treatment is aging an alkaline solution for 30 minutes while stirring at 65 ℃.
4. The method for preparing the fly ash-based hydrotalcite like compound according to claim 1, wherein the hydrothermal treatment is carried out at 70 ℃ for 12 hours.
5. A fly ash-based hydrotalcite like compound prepared by the method of any one of claims 1 to 4.
6. Use of the fly ash-based hydrotalcite like compound according to claim 5 for the adsorption of nitrate nitrogen.
7. The use of the fly ash-based hydrotalcite like compound according to claim 5 as an artificial wetland filler, wherein the artificial wetland filler further comprises iron powder and activated carbon powder.
8. The use according to claim 7, wherein the mass ratio of fly ash based hydrotalcite like compound, iron powder and activated carbon powder is 2:2:1.
9. The use according to claim 7, further comprising planting reed on the constructed wetland when removing nitrate nitrogen from the constructed wetland filler with fly ash based hydrotalcite-like compounds.
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