CN113292205A - Heavy metal polluted water body remediation method combining filter column and phytoremediation - Google Patents
Heavy metal polluted water body remediation method combining filter column and phytoremediation Download PDFInfo
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for restoring heavy metal polluted water by combining a filter column with phytoremediation. The ore forming pellet filter column can remove heavy metals through various mechanisms such as adsorption and mineralization of the multi-core shell ore forming pellets, continuously provide a nitrogen source for the subsequent deeply-repaired aquatic plants, promote the growth of the aquatic plants, and ensure the long-acting and stable repairing effect and the restoration of the ecological function of a water body. The method has wide application prospect in the aspect of removing heavy metal ions in the polluted water, all used materials are simple and easy to obtain, and the method is pollution-free, low in cost and wide in application range. The filtration of the filter column is combined with the restoration of aquatic plants so as to remove heavy metals in the water body efficiently and in a long-acting manner and restore the ecological function of the water body.
Description
Technical Field
The application belongs to the technical field of polluted water restoration, and particularly relates to a heavy metal polluted water body restoration method combining a filter column and phytoremediation.
Background
Heavy metal pollution in water mainly comes from two parts: natural sources and man-made sources. The natural source is mainly a rock weathered debris product, and heavy metals entering a water body through a natural way generally cannot cause pollution to the water body; the artificial pollution sources mainly comprise mining and metal smelting processing, chemical engineering, waste battery treatment, electronics, leather making, dyes, atmospheric dry and wet sedimentation, pesticide and fertilizer use and the like, and are the main reasons for causing heavy metal pollution of water bodies.
At present, the method for treating the heavy metal polluted water body comprises a physical method, a chemical method and a biological method. The physical method is mainly a dilution method, but is only suitable for small water bodies and is easy to cause pollution range diffusion. Chemical methods are classified into coagulation sedimentation, ion reduction, exchange, and electrokinetic remediation techniques. The coagulating sedimentation method mainly comprises the step of adding an alkaline substance into a water body polluted by heavy metal to enable heavy metal ions to generate hydroxides for sedimentation, but the sediment has the risk of secondary precipitation of the heavy metal in the water body. The ion reduction method and the ion exchange method are used for reducing the concentration of heavy metal in the water body by adding chemical agents, but have small application range and are easy to cause secondary pollution. The biological method is phytoremediation and microbial remediation, has a good effect of removing heavy metals, is green and environment-friendly, but takes long time, and has a general effect on high-concentration heavy metal polluted water. How to improve the feasibility and effectiveness of biological methods is a hot issue worthy of research.
Disclosure of Invention
The application aims to provide a heavy metal polluted water body restoration method combining a filter column and phytoremediation, harmful heavy metals in a water body are removed, the ecological function of the water body is restored, and finally environment-friendly water environment restoration is achieved.
In order to achieve the purpose, the technical scheme of the application is as follows:
a heavy metal polluted water body restoration method combining filter columns and phytoremediation comprises the following steps:
preparing multi-core shell ore-forming pellets with the functions of ore-forming and heavy metal solidification, and filling the prepared multi-core shell ore-forming pellets into a filter column;
pumping the heavy metal polluted water from the bottom of the filter column, wherein the multi-core shells in the heavy metal polluted water flow filter column form ore pellets, and the ore pellets flow out from the upper part of the filter column;
and the heavy metal polluted water treated by the filter column flows out of the upper part of the filter column and is discharged into a water body in which aquatic plants are planted for secondary restoration.
Further, the preparation method of the multi-core shell ore-forming pellet comprises the following steps:
adding gelatin and urea into deionized water, and mechanically stirring to obtain a uniform mixed solution;
adding the mixed solution into the uniformly stirred light liquid paraffin and span, continuously stirring, then adding glutaraldehyde for curing and crosslinking, dehydrating, filtering and washing the obtained product, and freeze-drying to obtain urea microspheres;
adding sodium alginate and urease into deionized water, stirring to dissolve, adding the urea microspheres, and dripping CaCl into the solution containing urea microspheres2And (4) crosslinking the solution, filtering and washing the obtained product to obtain the multi-core shell ore-forming pellet.
Furthermore, the mass ratio of the gelatin to the urea is 1 (2-3), the mass content of the gelatin in the mixed solution is 10 wt% -15 wt%, and the mass content of the urea in the mixed solution is 20 wt% -30 wt%.
Further, the volume ratio of the glutaraldehyde in the reaction solution is 1% (v/v) to 1.5% (v/v), and the crosslinking time is 1h to 1.5 h.
Further, isopropanol is selected for dehydration, and acetone is selected for washing.
Further, the mass ratio of the sodium alginate to the urease is (1-2): (1-3), the mass content of the sodium alginate in the solution added with the urea microspheres is 1 wt% -2 wt%, and the mass content of the urease in the solution added with the urea microspheres is 1 wt% -3 wt%.
Furthermore, the mass content of the urea microspheres in the solution added with the urea microspheres is 4 wt% -5 wt%.
Further, the CaCl2The mass concentration of the solution is 1% (w/v) -2% (w/v), the curing time is 30-45 min, and the diameter of the prepared multi-core shell mineral-forming pellet is 3.2-3.7 mm.
Further, the uniformly stirred light liquid paraffin and span are mixed, wherein the volume ratio of the paraffin is 80% (v/v) to 90% (v/v), and the mass content of the span is 2 wt% -3 wt%.
Furthermore, the flow velocity of the heavy metal polluted water body entering each filtering column is 1-5 per mill of the volume of the filtering column per minute.
The application provides a method for restoring heavy metal polluted water by combining a filter column with phytoremediation, the prepared multi-core shell ore-forming pellets are used as filler to prepare a packed filter column, and the heavy metal polluted water firstly passes through the pellet filter column, and then flows into a downstream pond to carry out phytoremediation deeply. The ore forming pellet filter column can remove heavy metals through various mechanisms such as adsorption and mineralization of the multi-core shell ore forming pellets, continuously provide a nitrogen source for the subsequent deeply-repaired aquatic plants, promote the growth of the aquatic plants, and ensure the long-acting and stable repairing effect and the restoration of the ecological function of a water body. The technical scheme of the application has wide application prospect in the aspect of removing heavy metal ions in the polluted water. All the materials used in the method are simple and easy to obtain, and the method is pollution-free, low in cost and wide in application range. The filtration of the filter column is combined with the restoration of aquatic plants so as to remove heavy metals in the water body efficiently and in a long-acting manner and restore the ecological function of the water body.
Drawings
FIG. 1 is a flow chart of a heavy metal polluted water body remediation method combining filtration column and phytoremediation according to the present application;
FIG. 2 is a flow chart of the preparation of multi-core shell ore-forming pellets;
FIG. 3 is a schematic diagram of a multi-core shell ore-forming pellet filter column in combination with phytoremediation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
This application filters the filter column and allies oneself with the aquatic plant restoration antithetical couplet to high efficiency, long-term heavy metal of getting rid of water and resume its ecological function. Calcite is a calcium carbonate mineral, and according to research, the calcite has strong adsorption effect on a plurality of harmful heavy metals such As As, Cr, Cd and Cu, can effectively solidify the heavy metals, and can not easily precipitate the adsorbed heavy metals again due to the change of external environment. The urea is now decomposed by the preparation of urease, producing
And
using Ca2+And
forming calcite minerals to adsorb and solidify heavy metals in the environment. Phytoremediation is the removal of heavy metals from the environment through plant absorption, plant volatilization, plant stabilization, rhizosphere filtration, and other actions. However, the heavy metal polluted water with high concentration can generate certain toxic action on plants, so that the removal efficiency is low, and the normal growth of the plants is damaged.
The urea microspheres coated by the prepared multi-core shell ore-forming pellets are decomposed by urease to slowly release urea to form calcite minerals, and the heavy metals in the water body are subjected to primary treatment, so that the concentration of the heavy metals is greatly reduced; and then the residual heavy metal in the water body is subjected to secondary treatment through phytoremediation, so that the harmful heavy metal in the water body can be deeply removed.
In one embodiment, as shown in fig. 1, a method for remediating a heavy metal contaminated water body by using a filter column and phytoremediation, comprises the following steps:
s1, preparing multi-core shell ore-forming pellets with the functions of ore-forming and solidifying heavy metals, and filling the prepared multi-core shell ore-forming pellets into a filter column;
s2, pumping the heavy metal polluted water from the bottom of the filter column, wherein the multi-core shells in the heavy metal polluted water flow filter column form ore pellets and flow out from the upper part of the filter column;
and step S3, the heavy metal polluted water treated by the filter column flows out of the upper part of the filter column and is discharged into a water body for planting aquatic plants for secondary restoration.
The multi-core shell ore-forming pellet filter column is prepared by fully mixing sodium alginate, urease and urea microspheres, and dripping CaCl2And (3) crosslinking the solution to form multi-core shell ore-forming pellets, and filling the multi-core shell ore-forming pellets into a corrosion-resistant material filter column, wherein the filter column can be selected from PVC, PMMA and ABS. The plant is aquatic plant with heavy metal treating function, and has long life and easy replacement, such as water hyacinth, water lettuce, duckweed, etc.
Filling the multi-core shell ore-forming pellets into a filter column, pumping polluted water containing harmful heavy metals such As As, Cr, Cd, Cu and the like from the bottom of the filter column, enabling the multi-core shell ore-forming pellets in the heavy metal polluted water flow filter column, and decomposing urea microspheres slowly-released urea catalytically coated by urease in the multi-core shell ore-forming pellets into urea
And
can be mixed with Ca in the multi-core pellet and the water body2+The combination forms calcite, thereby adsorbing and fixing harmful heavy metals such As As, Cr, Cd, Cu and the like
Can directly form insoluble precipitate with some heavy metal ions, and the alginate on the multi-core shell ore-forming pellet can be used for treating some heavy metal ions such as Cd2+Has strong adsorption effect. The heavy metal polluted water treated by the filter column flows out from the upper part of the filter column and is discharged into the polluted water part where the aquatic plants are plantedThe water treatment pool is repaired for the second time, and the aquatic plants can remove the heavy metals remained in the polluted water through the actions of plant absorption, plant volatilization, plant stabilization, rhizosphere filtration and the like.
In practical application, the filling filter columns with different sizes can be customized according to the flow of the treated heavy metal polluted water body, and the flow rate is controlled to be 1-5 per mill of the volume of the filter column per minute. In order to achieve the maximum removal efficiency, the filled multi-core shell ore-forming pellets are replaced once in 10 to 15 days after the filter column is filled. The shape of the aquatic plant can be observed, and if the aquatic plant is rotten, the aquatic plant can be salvaged and replaced.
In one embodiment of the present application, as shown in fig. 2, the preparation method of the multi-core shell mineralized pellet is as follows:
adding gelatin and urea into deionized water, and mechanically stirring to obtain a uniform mixed solution;
adding the mixed solution into the uniformly stirred light liquid paraffin and span, continuously stirring, then adding glutaraldehyde for curing and crosslinking, dehydrating, filtering and washing the obtained product, and freeze-drying to obtain urea microspheres;
adding sodium alginate and urease into deionized water, stirring to dissolve, adding the urea microspheres, and dripping CaCl into the solution containing urea microspheres2And (4) crosslinking the solution, filtering and washing the obtained product to obtain the multi-core shell ore-forming pellet.
In the embodiment, the mass ratio of the gelatin to the urea is 1 (2-3), the mass content of the gelatin in the mixed solution is 10 wt% -15 wt%, and the mass content of the urea in the mixed solution is 20 wt% -30 wt%. Where wt% is a unit of weight (mass) percent and represents the weight ratio, i.e., the specific gravity of a substance in a mixture.
The volume ratio of the glutaraldehyde in the reaction solution is 1% (v/v) to 1.5% (v/v), and the crosslinking time is 1h to 1.5 h. Wherein v/v represents the volume ratio and h is an hour unit.
The dehydration adopts isopropanol to carry out dehydration, and the washing adopts acetone to wash.
The mass ratio of the sodium alginate to the urease is (1-2): (1-3), the mass content of the sodium alginate in the solution added with the urea microspheres is 1 wt% -2 wt%, and the mass content of the urease in the solution added with the urea microspheres is 1 wt% -3 wt%.
The mass content of the urea microspheres in the solution added with the urea microspheres is 4 wt% -5 wt%.
The CaCl is2The mass concentration of the solution is 1% (w/v) -2% (w/v), the curing time is 30-45 min, and the diameter of the prepared multi-core shell mineral-forming pellet is 3.2-3.7 mm. Wherein w/v is the ratio of mass to volume, min is in units of minutes, and mm is in units of millimeters.
The evenly stirred light liquid paraffin and span are mixed, wherein the volume ratio of the paraffin is 80% (v/v) to 90% (v/v), and the mass content of the span is 2 wt% -3 wt%.
The flow velocity of the heavy metal polluted water entering each filtering column is 1-5 per mill of the volume of the filtering column per minute.
This application verifies the technical effect of this application technical scheme through specific experiment, in experiment 1:
50.0g of urea and 10.0g of gelatin were weighed into a round-bottomed flask containing 100mL of distilled water and subjected to a water bath at 50 ℃. Stirring and dissolving to obtain a uniform solution; putting 200.0mL of light liquid paraffin into a 500mL round-bottom flask, adding 4.0g of span-80 under the condition of 50 ℃ water bath, and stirring to obtain a uniform solution; 40mL of gelatin-urea solution was added under continuous stirring at 900r/min and stirred for 10 min. The whole round-bottom flask device is placed in an ice-water mixture at 4 ℃, and is further stirred for 30 min; to this mixed solution was slowly added 1mL of 50.0% (v/v) glutaraldehyde and stirring was continued for 1h to solidify. Adding 70mL of isopropanol, stirring for 20.0min, dehydrating, standing for 10.0min, filtering the obtained urea microspheres with acetone, washing, freeze-drying at (-40 deg.C, 48 hr), and storing in a self-sealing bag for use.
Adding 1.0g of sodium alginate and 1.0g of urease into 100mL of deionized water in a 500mL three-neck flask, stirring for 20min, adding 4.0g of urea microspheres, continuously stirring for 10min, pumping the mixed solution into a 2.0% solution through a single-channel peristaltic pump, curing for 30min, washing with deionized water, and filtering. Obtaining the small balls with the diameter of 3.2-3.7 mm. Filling the multinuclear shell ore-forming pellets into a PVC filter column with the inner diameter of 2cm and the height of 10 cm.
Obtaining heavy metal polluted water: the heavy metal polluted water comes from the tailing leaching water of a certain mining area in Xinjiang. The method comprises the following specific steps: weighing 20-100 g of sample according to the water content of the solid waste, drying at 105 ℃, and calculating the water content of the sample. Weighing a sample with the dry basis weight of 100g, placing the sample in a 2L extraction bottle, calculating the volume of a required leaching agent according to the water content of the sample and the liquid-solid ratio of 10: 1(L/kg), adding the leaching agent, tightly covering a bottle cap, vertically fixing the bottle cap on a horizontal oscillation device, adjusting the oscillation frequency to be 110 +/-10 times/min and the amplitude to be 40mm, taking down the extraction bottle after oscillating for 8 hours at room temperature, standing for 16 hours, and performing suction filtration to obtain heavy metal polluted water containing As, Cd, Cu and Cr. The concentrations of As, Cd, Cu and Cr in the contaminated water were measured to be about 10.33. mu.g/L, 0.38. mu.g/L, 13.62. mu.g/L and 1.78. mu.g/L, respectively. In order to better explore the removal effect, heavy metal polluted water is labeled, so that the inlet water concentration of As, Cd, Cu and Cr is 2.50 mg/L.
Culturing aquatic plants: selecting water hyacinth with approximate volume, placing in a water basin of a laboratory, acclimating for 14d, and carrying out 12h light and 12h dark treatment every day, wherein the culture medium used in the acclimation process is 2/5 Hoagland culture solution. The experimental water is purified water passing through a 0.45 mu m filter membrane, and the water temperature is controlled at 25 +/-3 ℃. The control group and the experimental group maintained the same culture conditions.
The packed filter column and the water hyacinth are combined to treat the heavy metal polluted water: pumping the polluted water containing heavy metals of As, Cd, Cu and Cr from the bottom of the filter column, making the polluted water flow through the ore-forming pellets, flowing out from the upper part of the filter column and discharging into a closed water body for planting hyacinth. Three water hyacinth plants are planted in the water flowing in each filling filter column. The experimental time was 20 days and the apparatus is shown in FIG. 3.
Determination of experimental results: after 20 days of the experiment, the quality of As, Cd, Cu and Cr of the ore-forming pellets and the roots and leaves of the water hyacinth in the packed filter column is measured. The analysis results show that the treatment amounts of As, Cd, Cu and Cr respectively account for 75.62%, 81.83%, 85.56% and 82.17% of the theoretical introduction amount. Considering errors, the effect of treating the heavy metal polluted water by combining the multi-core shell ore-forming pellet packed column and the water hyacinth is good.
In experiment 2, different from experiment 1, the packed filter column was not used in combination with aquatic plants, and the concentrations of As, Cd, Cu and Cr in the effluent were measured every day and compared with the influent concentration to calculate the removal rate. In the 20-day experiment, the removal rates of As, Cd, Cu and Cr are gradually reduced from 94.11%, 94.51%, 96.12% and 94.89% to 75.00%, 80.32%, 82.69% and 81.53% respectively in the first 10 days. From 10 th to 15 th days, the removal rates of As, Cd, Cu and Cr are greatly reduced to 50%, 59.66%, 55.11% and 57.92% respectively. The reduction of As, Cd, Cu and Cr removal rate gradually becomes gradual after 15 days.
The multi-core shell ore-forming pellets are filled into a filter column, heavy metal polluted water is pumped from the bottom of the filter column, the multi-core shell ore-forming pellets in the heavy metal polluted water flow filter column are catalyzed by urease in the multi-core shell ore-forming pellets to slowly release urea in coated urea microspheres, and the urea is decomposed into urea
And
can form ore pellets with multi-core shells and Ca in water body2+Combined to form calcite, thereby adsorbing and fixing harmful heavy metals
The alginate directly forms insoluble precipitate with some heavy metal ions, and the alginate on the multi-core shell mineral microsphere has strong adsorption effect on some heavy metal ions. Warp beamHeavy metal polluted water treated by the filter column flows out of the upper part of the filter column and is discharged into a water body in which aquatic plants are planted for secondary restoration, the aquatic plants can remove residual heavy metals in the polluted water through the actions of plant absorption, plant volatilization, plant stabilization, rhizosphere filtration and the like, and the polluted water treated by the multi-core shell ore-forming filter column contains a large amount of N elements and can be used as a nitrogen source of the aquatic plants to promote the growth and development of the plants.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The heavy metal polluted water body restoration method combining the filter column with the phytoremediation is characterized by comprising the following steps of:
preparing multi-core shell ore-forming pellets with the functions of ore-forming and heavy metal solidification, and filling the prepared multi-core shell ore-forming pellets into a filter column;
pumping the heavy metal polluted water from the bottom of the filter column, wherein the multi-core shells in the heavy metal polluted water flow filter column form ore pellets, and the ore pellets flow out from the upper part of the filter column;
and the heavy metal polluted water treated by the filter column flows out of the upper part of the filter column and is discharged into a water body in which aquatic plants are planted for secondary restoration.
2. The method for remediating a heavy metal polluted water body by combining a filter column with phytoremediation as claimed in claim 1, wherein the preparation method of the multi-core synthetic ore pellet is as follows:
adding gelatin and urea into deionized water, and mechanically stirring to obtain a uniform mixed solution;
adding the mixed solution into the uniformly stirred light liquid paraffin and span, continuously stirring, then adding glutaraldehyde for curing and crosslinking, dehydrating, filtering and washing the obtained product, and freeze-drying to obtain urea microspheres;
adding sodium alginate and urease into deionized water, stirring to dissolve, adding the urea microspheres, and dripping CaCl into the solution containing urea microspheres2And (4) crosslinking the solution, filtering and washing the obtained product to obtain the multi-core shell ore-forming pellet.
3. The method for restoring the heavy metal polluted water body by combining the filter column with the plant restoration according to claim 2, wherein the mass ratio of gelatin to urea is 1 (2-3), the mass content of gelatin in the mixed solution is 10 wt% -15 wt%, and the mass content of urea in the mixed solution is 20 wt% -30 wt%.
4. The method for remediating the heavy metal polluted water body by combining the filter column with the plant remediation as recited in claim 2, wherein the volume ratio of the glutaraldehyde in the reaction solution is 1% (v/v) to 1.5% (v/v), and the crosslinking time is 1h to 1.5 h.
5. The method for remediating a heavy metal polluted water body by combining a filter column with phytoremediation as recited in claim 2, wherein the dehydration is performed by isopropanol, and the washing is performed by acetone.
6. The heavy metal polluted water body restoration method combining the filter column and plant restoration as claimed in claim 2, wherein the mass ratio of sodium alginate to urease is (1-2): (1-3), the mass content of the sodium alginate in the solution added with the urea microspheres is 1 wt% -2 wt%, and the mass content of the urease in the solution added with the urea microspheres is 1 wt% -3 wt%.
7. The method for remediating a heavy metal polluted water body by combining a filter column and phytoremediation as recited in claim 2, wherein the urea microspheres are contained in the solution containing the urea microspheres in an amount of 4 to 5 wt%.
8. The method for remediating a heavy metal contaminated water body using a combination of filter columns and phytoremediation as recited in claim 2, wherein the CaCl is2The mass concentration of the solution is 1% (w/v) -2% (w/v), the curing time is 30-45 min, and the diameter of the prepared multi-core shell mineral-forming pellet is 3.2-3.7 mm.
9. The heavy metal polluted water body restoration method combining the filter column and the plant restoration as recited in claim 2, characterized in that the light liquid paraffin and the span are uniformly stirred, wherein the volume ratio of the paraffin is 80% (v/v) to 90% (v/v), and the mass content of the span is 2 wt% to 3 wt%.
10. The method for remediating a heavy metal contaminated water body by using filter columns and phytoremediation as claimed in claim 1, wherein the flow rate of the heavy metal contaminated water body entering each filter column is 1-5% of the volume of the filter column per minute.
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