CN108911101B - Method for efficiently removing heavy metal ions based on ball milling oxalic acid zero-valent iron - Google Patents
Method for efficiently removing heavy metal ions based on ball milling oxalic acid zero-valent iron Download PDFInfo
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Abstract
The invention relates to a method for efficiently removing heavy metal ions based on ball milling of oxalic acid zero-valent iron. The method comprises the following steps: adding ball-milled oxalic acid zero-valent iron into an aqueous solution containing heavy metal ions to remove the heavy metal ions. The method for acidifying zero-valent iron by ball milling is characterized in that oxalic acid and zero-valent iron are prepared by a solid-phase ball milling method, the heavy metal ion removing capability of the method is obviously enhanced, and the problem of low activity of removing heavy metal ions by the zero-valent iron is solved. The preparation method of the oxalic acid zero-valent iron provided by the invention is simple, low in cost and environment-friendly, and can be widely used for treating underground water polluted by various heavy metals.
Description
Technical Field
The invention belongs to the field of environmental chemistry, and particularly relates to a method for efficiently removing heavy metal ions based on ball-milling oxalic acid zero-valent iron, which is applicable to treatment of wastewater in the fields of printing and dyeing, industry and the like.
Background
The use amount of heavy metals (chromium, arsenic, lead, cadmium, copper, nickel, zinc, tin, mercury and the like) is increasing in industry, agriculture, science and technology and daily life, and the heavy metals are released into the environment through various channels, so that the total heavy metal pollution amount in the environment is continuously increased. Heavy metal pollution is easy to accumulate, irreversible, high in toxicity, slow in metabolism, easy to enrich and the like, and seriously harms human health. Therefore, the development of green and efficient heavy metal pollution control technology is imminent.
Compared with other heavy metal pollution remediation technologies, the zero-valent iron technology has the characteristics of environmental friendliness, removal of various heavy metals and the like, and is widely applied to treatment of wastewater and polluted groundwater for twenty years. However, the surface of the zero-valent iron is easily oxidized by water and oxygen, and a layer of iron oxide is generated on the surface to form a unique core-shell framework. The thickness of the iron oxide shell layer and the functional groups on the surface of the iron oxide shell layer influence the adsorption and reduction of the heavy metals, the thickness of the oxidation layer influences the electron transmission rate, and the functional groups on the surface of the oxidation layer influence the adsorption of the heavy metals, so that the proportion of electrons transmitted by zero-valent iron for reducing the heavy metals, namely the electron selectivity, is determined. Researchers have developed various methods to eliminate the negative effects of the shell layer, such as (partially) removing the shell layer on the surface of the zero-valent iron by means of acid washing, reducing agent reduction, ultrasonic stripping, or applying a weak magnetic field to accelerate the corrosion rate of the zero-valent iron. The methods only reduce the thickness of the oxide layer through pretreatment, but the oxide layer is regenerated in the process of removing heavy metals, so that the problem of low activity of removing the heavy metals by zero-valent iron is difficult to solve through the removal of the oxide layer.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for efficiently removing heavy metal ions based on ball-milling grass acidified zero-valent iron.
The technical scheme adopted by the invention for solving the problems is as follows:
the ball-milling zero-valent iron oxalate based method for efficiently removing heavy metal ions comprises the steps of adding the ball-milling zero-valent iron oxalate into an aqueous solution containing the heavy metal ions to remove the heavy metal ions, wherein the ball-milling zero-valent iron oxalate is prepared by oxalic acid and the zero-valent iron through a solid-phase ball milling method.
According to the scheme, the oxalic acid and the zero-valent iron are subjected to ball milling, washing and vacuum drying to obtain the oxalic acid zero-valent iron. The washing is water washing and then alcohol washing.
According to the scheme, the mol percentage of oxalic acid in zero-valent iron is as follows: 0.2 to 2.0 percent.
According to the scheme, the ball milling time is as follows: 0.5-5h, and the ball milling rotating speed is 300-.
According to the scheme, the grain diameter, the appearance, the purity and the storage time of the zero-valent iron are not required. The zero-valent iron can be in micron-scale or nanometer-scale.
According to the scheme, the purity of the oxalic acid is industrial grade or above.
According to the scheme, the using amount of the ball-milling oxalic acid zero-valent iron is 1-5 g/L.
According to the scheme, the concentration of the heavy metal ions is 2-50ppm, the reaction temperature is 10-30 ℃, and the reaction pH is 4-8.
According to the scheme, the shaking table is used for shaking in the removing process, so that the heavy metal ions are fully contacted with zero-valent iron. Shaking the shaking table to ensure that the heavy metal ions are fully contacted with zero-valent iron. If the vibration is not carried out, a better effect can be obtained.
According to the scheme, the heavy metals include but are not limited to chromium, mercury, silver, lead and nickel.
Technical principle of the invention (see fig. 1):
the surface of the zero-valent iron is covered with a layer of hydroxyl, so that the adsorption capacity to heavy metal ions is poor, more zero-valent iron is oxidized by water and oxygen, and the hydroxyl on the surface of the zero-valent iron is not beneficial to the adsorption of the heavy metal ions. After oxalic acid and zero-valent iron are subjected to ball milling treatment, oxalate replaces surface hydroxyl and is chemically bonded to the surface of the zero-valent iron, and the oxalate modified on the surface of the zero-valent iron in situ can stably exist on the surface of the zero-valent iron. The oxalic acid on the surface of the zero-valent iron can improve the adsorption capacity to heavy metal ions, thereby improving the proportion of electrons of the zero-valent iron used for reducing the heavy metal ions, reducing the amount consumed by the reaction of the electrons of the zero-valent iron and water or oxygen, and realizing the efficient removal of the heavy metal ions. Experiments prove that the composite has high activity when used for removing different heavy metal ions.
The invention has the advantages that:
1. the method for efficiently removing the heavy metal ions based on the ball-milling oxalic acid zero-valent iron is simple and easy to operate, and can obviously improve the removal of the heavy metal ions.
2. The zero-valent iron has low price and is environment-friendly, and can be widely used in the actual treatment of heavy metal pollution.
3. The method of the invention has universal removal capability on different heavy metal ions.
Drawings
FIG. 1 is a schematic diagram of the preparation of ball-milled zero-valent iron oxalate;
FIG. 2 is a comparison graph of the activity of oxalic acid directly added in the processes of ball milling preparation of zero-valent iron oxalate and chromium removal of zero-valent iron in example 1;
FIG. 3 is a graph showing the effect of ball milling grass on treatment of hexavalent chromium in polluted water bodies by using zero-valent iron;
FIG. 4 is a diagram showing the effect of the ball-milled grass on the mercury in the water polluted by zero-valent iron;
FIG. 5 is a graph showing the effect of ball-milling zero-valent iron oxalate on treatment of silver in a polluted water body in example 4;
FIG. 6 is a diagram showing the effect of ball-milling zero-valent iron oxalate on treatment of lead in polluted water in example 5;
FIG. 7 is a diagram showing the effect of ball-milling zero-valent iron oxalate on treatment of nickel in polluted water in example 6;
Detailed Description
The following detailed description of the present invention is provided by way of specific embodiments, which are provided for illustration purposes and are not intended to limit the invention.
Example 1 comparative graph of effects of ball milling for preparing zero-valent iron oxalate and direct addition of oxalic acid in chromium removal process of zero-valent iron
5.6g of zero-valent iron (the particle size is maximally 80 μm) and 0.126g of oxalic acid (containing dihydrate) are placed in a ball milling pot, the rotating speed is 550r/min, the ball milling time is 2h, and then the sample is washed by water, alcohol and dried in vacuum to obtain the oxalic acid zero-valent iron Fe/Ox (n is 1.0%). 30mL of potassium dichromate solution with hexavalent chromium concentration of 20mg/L is used for simulating chromium-containing wastewater, the pH of the solution is 6.5, the temperature is 25 ℃, 0.1g of Fe/Ox sample is added, the solution is placed into a shaking table with the rotating speed of 150r/min, the sample is taken periodically, and the concentration of the hexavalent chromium in the solution is measured by a spectrophotometry method. As a control experiment, 0.097g of Fe theoretically contained in a sample of 0.1g of Fe/Ox (n ═ 1.0%) and 0.003g of oxalic acid (oxalic acid concentration 0.79mmol/L) were added to the chromium solution, and the solution pH was adjusted to 6.5. As a further control experiment, 0.1g of zero-valent iron was added, and different amounts of oxalic acid (oxalic acid concentration in the system was 0.01, 0.1mol/L, respectively) were added as control experiments, and the pH of the solution was adjusted to 6.5, and the other conditions were unchanged, and the results are shown in FIG. 2. The zero-valent iron oxalate almost completely removes chromium within 120 min; while 0.003g of oxalic acid is directly added into the chromium removal system, and only about 10 percent of oxalic acid is removed after reaction for 120 min; with the sequential increase of the amount of oxalic acid, the chromium removal activity is enhanced, but still significantly lower than zero-valent iron oxalate.
Fully demonstrated above, the invention can realize the high-efficiency removal of chromium by the oxalic acid and the zero-valent iron oxalate prepared by the zero-valent iron solid-phase ball milling method.
Example 2 ball-milling effect diagram for treating hexavalent chromium in polluted water by oxalic acid zero-valent iron
5.6g of zero-valent iron (the grain diameter is maximally 160 mu m) and different oxalic acid amounts (the molar ratio of oxalic acid to zero-valent iron is 0%, 0.2%, 0.5%, 1.0% and 2.0% in sequence) are put into a ball milling pot, the rotating speed is 550r/min, the ball milling time is 2h, a sample is washed by water, alcohol and dried in vacuum, and the oxalic acid zero-valent iron, namely Fe/Ox (n is 0.0%, 0.2%, 0.5%, 1.0% and 2.0%) is obtained. 30mL of potassium dichromate solution with hexavalent chromium concentration of 20mg/L is used for simulating chromium-containing wastewater, the pH of the solution is 5.2, the temperature is 30 ℃, 0.1g of Fe/Ox sample is added, the solution is placed into a shaking table with the rotating speed of 150r/min, sampling is carried out periodically, and the concentration of hexavalent chromium in the solution is measured by a spectrophotometry method, and the result is shown in figure 3. The non-oxalic acid zero-valent iron is only removed by 10% within 120min, the chromium removal rate of the oxalic acid zero-valent iron is greatly improved, and the chromium removal rate is sequentially increased along with the sequential increase of the ball milling oxalic acid amount, which shows that the modification of different oxalic acids can achieve the efficient removal of chromium.
Example 3 effect diagram of treating mercury in polluted water body by ball milling grass acidified zero-valent iron
5.6g of zero-valent iron (the particle size is maximally 80 μm) and 0.126g of oxalic acid (containing dihydrate) are put into a ball milling pot, the rotating speed is 550r/min, the ball milling time is 2h, and the mixture is washed by water, alcohol and dried in vacuum to obtain the oxalic acid zero-valent iron, namely Fe/Ox (n is 1.0%). The mercury concentration in the solution was measured by inductively coupled plasma emission spectrometer, and the result of the control experiment using non-oxalic acid zero valent iron is shown in fig. 4, while using 30mL of mercury chloride solution with 5mg/L mercury concentration to simulate mercury wastewater, the solution pH is 7.0, the temperature is 25 ℃, 0.1g of Fe/Ox sample is added, the shaking table with 150r/min rotation speed is used to periodically sample, and the mercury concentration in the solution is measured by using non-oxalic acid zero valent iron. Non-oxalated zero-valent iron slowly removed mercury within 120min, while oxalated zero-valent iron had completely removed mercury within 10 min. The oxalic acid zero-valent iron can achieve the high-efficiency mercury removal.
Example 4 effect diagram of treating silver in polluted water by ball milling zero-valent iron oxalate
5.6g of zero-valent iron (the particle size is maximally 40 mu m) and 0.126g of oxalic acid (containing dihydrate) are put into a ball milling pot, the rotating speed is 550r/min, the ball milling time is 2h, and the mixture is washed by water, alcohol and dried in vacuum to obtain the oxalic acid zero-valent iron, namely Fe/Ox (n is 1.0%). Silver nitrate solution with silver concentration of 5mg/L (30 mL) is used to simulate silver wastewater, the pH of the solution is 6.5, the temperature is 25 ℃, Fe/Ox sample of 0.1g is added, the solution is put into a shaking table with the rotating speed of 150r/min, sampling is carried out periodically, the silver concentration in the solution is measured, meanwhile, zero-valent iron which is not oxalic acid is used as a control experiment, and the result is shown in figure 5. Non-oxalated zero-valent iron was able to slowly remove silver within 120min, whereas oxalated zero-valent iron had completely removed silver within 10 min. The oxalic acid zero-valent iron can achieve the high-efficiency removal of silver.
Example 5 Effect diagram of ball-milling zero-valent iron oxalate in treatment of lead in polluted water
5.6g of zero-valent iron (the particle size is maximally 80 μm) and 0.126g of oxalic acid (containing dihydrate) are put into a ball milling pot, the rotating speed is 550r/min, the ball milling time is 1h, and the mixture is washed by water, alcohol and dried in vacuum to obtain the oxalic acid zero-valent iron, namely Fe/Ox (n is 1.0%). 30mL of lead nitrate solution with lead concentration of 10mg/L is used for simulating lead wastewater, the pH of the solution is 6.5, the temperature is 25 ℃, 0.1g of Fe/Ox sample is added, the solution is placed into a shaking table with the rotating speed of 150r/min, sampling is carried out periodically, the lead concentration in the solution is measured, meanwhile, zero-valent iron which is not oxalic acid is used as a control experiment, and the result is shown in figure 6. The lead removal rate constant of the oxalated zero-valent iron is 2 times that of the non-oxalated zero-valent iron, which shows that the oxalated zero-valent iron can achieve the high-efficiency lead removal.
Example 6 effect diagram of ball milling of zero-valent iron oxalate for treatment of nickel in polluted water
5.6g of zero-valent iron (the particle size is 160 μm at most) and 0.252g of oxalic acid (containing dihydrate) are placed in a ball milling pot, the rotating speed is 800r/min, the ball milling time is 4h, and a sample is washed by water, alcohol and dried in vacuum to obtain the oxalic acid zero-valent iron, namely Fe/Ox (n is 2.0%). 50mL of nickel chloride solution with the nickel concentration of 20mg/L is used for simulating nickel wastewater, the pH value of the solution is 8, 0.05g of Fe/Ox sample is added, the solution is placed into a shaking table with the rotating speed of 400r/min, the temperature is 10 ℃, samples are taken periodically, the concentration of residual nickel in the solution is measured, meanwhile, zero-valent iron which is not oxalic acid is used as a control experiment, and the result is shown in figure 7. 98% of oxalated zero-valent iron is removed within 40min, and only 60% of non-oxalated zero-valent iron is removed within 90min, which indicates that the oxalated zero-valent iron can achieve high-efficiency removal of nickel.
Claims (7)
1. A method for efficiently removing heavy metal ions based on ball milling oxalic acid zero-valent iron is characterized by comprising the following steps: adding ball-milling zero-valent iron oxalate into an aqueous solution containing heavy metal ions to remove the heavy metal ions, wherein the ball-milling zero-valent iron oxalate is prepared by oxalic acid and micron-sized zero-valent iron through a solid-phase ball milling method, and the mol percentage of the oxalic acid in the zero-valent iron is as follows: 0.2-2.0%, and the ball milling time is as follows: 0.5-5h, and the ball milling rotating speed is 300-.
2. The method of claim 1, wherein: and after ball milling, washing and vacuum drying the oxalic acid and the zero-valent iron to obtain the oxalic acid zero-valent iron.
3. The method of claim 1, wherein: the purity of the oxalic acid is industrial grade or above.
4. The method of claim 1, wherein: the dosage of the ball-milling oxalic acid zero-valent iron is 1-5 g/L.
5. The method of claim 1, wherein: the concentration of the heavy metal ions is 2-50ppm, and the reaction temperature is 10-30oAnd C, the reaction pH is 4-8.
6. The method of claim 1, wherein: and in the removing process, shaking by using a shaking table to ensure that the heavy metal ions are fully contacted with zero-valent iron.
7. The method of claim 1, wherein: the heavy metal is selected from chromium, mercury, silver, lead and nickel.
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