CN111807630A - High-efficient molybdenum-removing vertical subsurface flow constructed wetland purification device - Google Patents
High-efficient molybdenum-removing vertical subsurface flow constructed wetland purification device Download PDFInfo
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 41
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- 230000010355 oscillation Effects 0.000 claims description 2
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- 241001465754 Metazoa Species 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device which comprises a water inlet mechanism, a purification area and a water outlet mechanism, wherein the purification area sequentially comprises a soil layer, a composite matrix layer, a fine sand layer and a supporting layer from top to bottom, the composite matrix layer is a combined matrix of modified coal cinder and pyrite, and plants are planted in the soil layer; the purification area top is provided with water inlet mechanism, the purification area bottom is provided with out water mechanism. The composite substrate is used as one of the components of the packing layer, and has the advantages of high molybdenum removal efficiency, wide source, low price, easy obtaining, simple and convenient preparation and the like. The invention combines the adsorption material with the artificial wetland, has high efficiency for removing heavy metal molybdenum sewage, and the concentration of molybdenum in the effluent of the artificial wetland meets the quality standard of groundwater in China.
Description
Technical Field
The invention relates to the technical field of artificial wetland sewage ecological treatment, in particular to a vertical subsurface flow artificial wetland purification device capable of efficiently removing molybdenum.
Background
Molybdenum (Mo) is one of transition elements with biological activity, is also a trace element necessary for animals and plants, and is beneficial to normal physiological activities of living bodies when taken in a proper amount. However, once excessive molybdenum intake occurs, the health of the organism is impaired, and even molybdenum poisoning of the organism is caused. The limit value of the mass concentration of molybdenum in specific projects of the surface water source of centralized domestic drinking water in the sanitary standards of domestic drinking water and the quality standards of surface water environment of China is 0.07mg L-1. The hexavalent molybdate ion (Mo (VI)) is relatively stable in the environment and is easily taken up by organisms in most systems, so that the Mo (VI) concentration in the aqueous solution is more than 5ppm, which is harmful to the environment. In industrial applications, molybdenum has significant economic value as a component of fertilizers, catalysts, metal alloys, and rust inhibitors. However, the molybdenum ore mining technology is relatively lagged behind, and the management strength of the alkaline molybdenum tailings is insufficient, so that the molybdenum pollution of water bodies in parts of domestic and foreign areas is relatively serious.
At present, the domestic molybdenum sewage treatment method mainly comprises four types, namely an ion exchange method, a chemical precipitation method, an adsorption method, an artificial wetland method and the like. The ion exchange method has the defects of high cost and difficult operation and maintenance, while the chemical precipitation method is easy to generate secondary pollution, and the adsorption method is widely applied but not suitable for the treatment requirement of molybdenum non-point source pollution. The artificial wetland is a water treatment ecosystem constructed by simulating a natural wetland. The process has the advantages of low construction and operation cost, simple and convenient management, relatively stable purification effect and the like, and is widely regarded.
The artificial wetland is a sewage treatment ecological engineering technology which is developed on the basis of degrading sewage by a natural wetland and realizes the purification of the sewage by utilizing the triple synergistic action of physics, chemistry and biology in a natural ecological system. Among them, the subsurface wetland system, i.e. the water seeps under the surface of the filler, can more fully utilize the surface of the filler and the biological membrane on the root system of the plant and other various actions to treat the waste water, and has good sanitary conditions, so the subsurface wetland system is widely adopted. The artificial wetland mainly depends on a substrate layer in a system for removing heavy metals, but the common artificial wetland substrate has low molybdenum removal efficiency, so that the development of a novel high-efficiency molybdenum-removing artificial wetland substrate is one of the focuses of research. The research on the substrate except molybdenum mainly focuses on the following at home and abroad: iron ore, soil, chelating resin, chitosan and activated carbon. Related studies have shown that substrates rich in iron and aluminum oxides with large surface areas provide good molybdenum removal. Because the molybdenum removing efficiency of the soil is extremely low, and the cost of materials such as chelating resin, chitosan, activated carbon and the like is expensive, the slag containing iron-aluminum oxide and having a large surface area can be a suitable material for the molybdenum removing artificial wetland substrate. Coal cinder as an industrial waste has a large specific surface area, but most of the coal cinder is alkaline and is not beneficial to removing molybdenum in a water body, so that the coal cinder is modified by adopting sulfuric acid. Meanwhile, pyrite with rich earth crust content is selected from the artificial wetland matrix of the research. Because the pyrite has the acid production function, and the rich sulfur and iron elements are beneficial to removing the molybdenum in the water body. However, the pyrite has a small specific surface area, so that the pyrite can be combined with the modified coal cinder with a large specific surface area to be used as the substrate of the artificial wetland to possibly achieve a good molybdenum removal effect.
There are many technical achievements about the artificial wetland sewage ecological treatment method, such as chinese patent No. CN105594642A, granted 2016, 05 and 25. The patent discloses a patent document named as 'a multi-stage surface flow artificial wetland ecological symbiotic system based on pool ridges and a using method'; chinese patent No. CN105600932A, granted on 2016, 05 and 25 months. The patent discloses a patent document entitled "a modular constructed wetland sewage treatment plant"; chinese patent No. CN102642978A, grant publication date 2012, 08 month 22. The patent discloses a patent document named as 'a high-efficiency circulating vertical flow constructed wetland and equipment suitable for sewage dispersion treatment'; chinese patent No. CN105600934A, granted on 2016, 05 and 25 months. This patent discloses a patent document entitled "a new type of constructed wetland". The wetland systems have good removal effect on specific pollutants, but the wetland structure is complex, and the operation and maintenance cost is relatively high.
Related invention patents also exist in the aspect of artificial wetland composite substrates. For example, chinese patent No. CN210163197U, publication grant No. 2020, 03, 20. The patent discloses a patent document entitled "an artificial wetland treatment device using composite filler"; chinese patent No. CN101293711B, issued on 2011/07/20/day. The patent discloses a patent document entitled "a rapid assembly type constructed wetland sewage treatment system and a filler unit thereof"; a patent document entitled "artificial wetland sewage treatment method based on modularized built-in interstitial filler" is disclosed in Chinese patent No. CN102765804B, granted publication No. 2014, 04 and 16; a patent document entitled "composite vertical subsurface flow constructed wetland sewage purification system based on functional filler structure" is disclosed in Chinese patent No. CN110790388A, granted publication No. 2020, 14.02/14. These artificial wetlands are mostly used for removing organic pollutants or inorganic non-metallic ions, and the treatment capacity of heavy metal anions is unknown.
In the aspect of adsorbing materials for removing heavy metal anions, such as Chinese patent No. CN106268720B, granted publication No. 2018, 09 and 11, a patent document named as a preparation method of a biochar composite adsorbing material for removing surface water molybdate is disclosed; chinese patent No. CN106423087A, granted publication No. 2017, No. 02, No. 22. The patent discloses a patent document entitled "preparation of magnetic chitosan carbon spheres and application thereof in adsorption removal of Cr (VI) in water"; chinese patent No. CN106582500A, granted publication No. 2017, 04/06/h. The patent discloses a patent document entitled "a Cr (VI) diatomite composite material capable of adsorbing and degrading and a preparation method thereof"; chinese patent No.: CN106622099A entitled "preparation of arsenic adsorption material and renaturation and reuse method thereof" in the publication of 2017, 05 and 10 months. Although the raw materials of the composite materials are cheap and easy to obtain, the composite materials have the defect of complex preparation process, and the adsorption efficiency is still to be improved.
Disclosure of Invention
The invention aims to solve the technical problem of developing a vertical subsurface flow constructed wetland purification device for efficiently removing molybdenum. The composite substrate is used as one of the components of the packing layer, and has the advantages of high molybdenum removal efficiency, wide source, low price, easy obtaining, simple and convenient preparation and the like. The invention combines the adsorption material with the artificial wetland, and has high removal efficiency on heavy metal molybdenum sewage.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device comprises a water inlet mechanism, a purification area and a water outlet mechanism, wherein the purification area sequentially comprises a soil layer, a composite matrix layer, a fine sand layer and a supporting layer from top to bottom, the composite matrix layer is a combined matrix of modified coal cinder and pyrite, and plants are planted in the soil layer; the purification area top is provided with water inlet mechanism, the purification area bottom is provided with out water mechanism.
Preferably, the water inlet mechanism adopts intermittent water inlet to simulate molybdenum tailing leachate caused by rainfall erosion, one week is a period, the total time of water inlet and treatment is 3-4 d, and the total time of emptying and idling is 3-4 d.
Preferably, the modified coal cinder is prepared by the following method: putting the coal cinder into clear water to wash for 1d, then grinding, rinsing, naturally drying, and screening to obtain the coal cinder with the particle size of 1-2 mm; 2.0-4.0 mol/L of H2SO4Adding the solution into the coal cinder, oscillating for 8-10 h at the oscillation speed of 200r/min, and washing with water until the solution does not contain SO4 2-And air-drying to obtain the product.
Preferably, the pyrite is prepared by the following method: and (3) washing the crude pyrite product for 1d by using clear water, then grinding, rinsing, naturally drying, and screening to obtain the pyrite with the particle size of 1-2 mm.
Preferably, the volume ratio of the modified coal slag to the pyrite is 5: 1-1: 1.
Preferably, the plant planted in the soil layer is typha orientalis.
Preferably, the planting density of the cattail is 20-30 plants/m2。
Preferably, the bearing layer comprises a fine gravel layer and a coarse gravel layer from top to bottom in sequence.
Preferably, go out water mechanism including being located the many outlet pipes of bearing layer bottom, be located in the bearing layer the outlet pipe has seted up a plurality of inlet openings on extending its length direction, be located outside the bearing layer install the outlet valve on the outlet pipe.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device, the adsorption material and the constructed wetland are combined to generate a comprehensive effect, the adsorption matrix material is wide in source and low in price, and the waste resource utilization can be achieved.
(2) The high-efficiency vertical subsurface flow composite matrix filler constructed wetland purification device has high removal efficiency of heavy metal molybdenum sewage, the average removal rate can reach more than 85.3 percent, and the outlet molybdenum concentration of the constructed wetland meets the IV (less than or equal to 0.5mg/L) of the national underground water quality standard (GB/T14848-93).
Drawings
FIG. 1 is a schematic structural diagram of a vertical subsurface flow constructed wetland purification device for efficiently removing molybdenum;
in the figure: 1-a water inlet mechanism; 2-a water inlet mechanism; 21-a water outlet mechanism; 22-a composite matrix layer; 23-fine sand layer; 24-a fine gravel layer; 25-a coarse gravel layer; 26-a plant; 3-and a water outlet mechanism; 31-a plant; 32-water inlet holes; 33-outlet valve.
Fig. 2 is a diagram of the removal rate of the artificial wetland system to the water body Mo (VI).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device suitable for molybdenum tailing non-point source sewage treatment, and as shown in fig. 1, the purification device comprises a water inlet mechanism 1, a purification area 2 and a water outlet mechanism 3, wherein the purification area 2 sequentially comprises a soil layer 21, a composite matrix layer 22, a fine sand layer 23 and a bearing layer from top to bottom.
The soil layer 21 is planted with typha officinalis with planting density of 26 plants/m2. The composite matrix layer 22 is a composite matrix of modified coal cinder and pyrite, and the supporting layer sequentially comprises a fine gravel layer 24 and a coarse gravel layer 25 from top to bottom.
The upper part of the purification area 2 is provided with a water inlet mechanism 1, and the bottom of the purification area 2 is provided with a water outlet mechanism 3. The water inlet mechanism 1 adopts intermittent water inlet to simulate molybdenum tailing leachate caused by rainfall erosion, one week is a period, the water inlet and treatment time is 4d, and the emptying and idle time is 3 d. The water outlet mechanism 3 comprises a plurality of water outlet pipes 31 positioned at the bottom of the bearing layer, a plurality of water inlet holes 32 are formed in the length direction of the water outlet pipes 31 positioned in the bearing layer, and water outlet valves 33 are arranged on the water outlet pipes 31 positioned outside the bearing layer.
Wherein the volume ratio of the modified coal cinder to the pyrite in the composite matrix layer is 3: 1.
The modified coal cinder is prepared by the following method: washing the coal slag in clear water for 1d, then grinding, rinsing, naturally drying, and screening to obtain the coal slag with the particle size of less than 2 mm; 4.0mol/L of H2SO4Adding the solution into the coal cinder, oscillating for 10h at a speed of 200r/min, and washing with water until no SO is contained4 2-And air-drying to obtain the product.
The pyrite is prepared by the following method: and (3) washing the crude pyrite product for 1d by using clear water, then grinding, rinsing, naturally drying, and screening to obtain the pyrite with the particle size of less than 2 mm.
Example 2
The same as example 1, except that the composite matrix layer was soil.
Example 3
The same as example 1, except that the composite matrix layer was modified coal slag.
Example 4
The same as example 1, except that the volume ratio of the modified coal slag to the pyrite in the composite matrix layer was 5: 1.
Example 5
The same as example 3, except that the feed water + treatment time was 2d, and the drain + idle time was 5d
The constructed wetlands of the above examples 1 to 5 were subjected to the molybdenum removal test, respectively.
For the corresponding wetland models, the constructed wetlands in examples 1-5 were placed in a cylindrical plastic bucket with a height of 60cm, a diameter of 25cm at the bottom and a diameter of 38cm at the top.
The composition and arrangement sequence of the vertical subsurface flow constructed wetland purification device for removing molybdenum with high efficiency in the models of the examples 1-5 is shown in the table 1.
TABLE 1 arrangement sequence of vertical subsurface flow constructed wetland purification device
Sodium molybdate (Na) for molybdenum as target contaminant of experiment2MoO4·2H2O), and the average concentration of the molybdenum in the inlet water is 3.2 mg/L. The effluent water sample is collected after 1min of effluent every time, the molybdenum content in the water sample is measured by a thiocyanate spectrophotometry, and the minimum detection concentration is 5 ug/L.
Test data of each device after operating for 3 months show that the constructed wetland system in the embodiments 1 to 5 of the invention has certain effect of removing molybdate in sewage. The removal rate of the molybdenum in the examples 1 and 4 is obviously higher than that in the examples 2, 3 and 5. Specifically, as shown in table 2.
TABLE 2 results of the molybdenum removal experiments for the different examples
Wherein, fig. 2 is a graph of the removal rate of molybdate in sewage in the artificial wetland system in the embodiment 1 at different times.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device is characterized by comprising a water inlet mechanism (1), a purification area (2) and a water outlet mechanism (3), wherein the purification area (2) sequentially comprises a soil layer (21), a composite matrix layer (22), a fine sand layer (23) and a bearing layer from top to bottom, the composite matrix layer (22) is a combined matrix of modified coal slag and pyrite, and plants (26) are planted in the soil layer (21); purification area (2) top is provided with into water mechanism (1), purification area (2) bottom is provided with out water mechanism (3).
2. The vertical subsurface flow constructed wetland purification device for efficiently removing molybdenum according to claim 1, characterized in that the water inlet mechanism (1) adopts intermittent water inlet to simulate molybdenum tailing leachate caused by rainfall erosion, one week is a period, the total time of water inlet and treatment is 3-4 d, and the total time of emptying and idling is 3-4 d.
3. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device of claim 1, wherein the modified coal slag is prepared by the following method: putting the coal cinder into clear water to wash for 1d, then grinding, rinsing, naturally drying, and screening to obtain the coal cinder with the particle size of 1-2 mm; 2.0-4.0 mol/L of H2SO4Adding the solution into the coal cinder, oscillating for 8-10 h at the oscillation speed of 200r/min, and washing with water until the solution does not contain SO4 2-And air-drying to obtain the product.
4. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device according to claim 1, wherein the pyrite is prepared by the following method: and (3) washing the crude pyrite product for 1d by using clear water, then grinding, rinsing, naturally drying, and screening to obtain the pyrite with the particle size of 1-2 mm.
5. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device of claim 1, wherein the volume ratio of the modified coal slag to the pyrite is 5: 1-1: 1.
6. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device as claimed in claim 1, wherein the plant (26) planted in the soil layer (21) is typha orientalis.
7. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device as claimed in claim 6, wherein the planting density of the cattail is 20-30 plants/m2。
8. The apparatus for purifying the vertical subsurface flow constructed wetland with high efficiency for removing molybdenum according to claim 1, characterized in that the supporting layer comprises a fine gravel layer (24) and a coarse gravel layer (25) from top to bottom in sequence.
9. The high-efficiency molybdenum-removing vertical subsurface flow constructed wetland purification device as claimed in claim 1, wherein the water outlet mechanism (3) comprises a plurality of water outlet pipes (31) positioned at the bottom of the bearing layer, the water outlet pipes (31) positioned in the bearing layer are provided with a plurality of water inlet holes (32) along the length direction, and the water outlet pipes (31) positioned outside the bearing layer are provided with water outlet valves (33).
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