CN111871368A - Adsorbing material for removing rare metal ions in wastewater and preparation method thereof - Google Patents
Adsorbing material for removing rare metal ions in wastewater and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an adsorbing material for removing rare metal ions in wastewater and a preparation method thereof. The technical scheme is as follows: and (3) placing the expanded graphite in mixed acid according to the concentration of 8-9 g/L, ultrasonically stirring, carrying out solid-liquid separation, washing, and drying for 2-4 h to obtain the carboxylated expanded graphite. Blending according to the mass ratio of 1: 40-60 of carboxylated expanded graphite to R-alkene-n-amine, mixing, ultrasonically stirring, carrying out oil bath, washing, carrying out solid-liquid separation, drying and grinding to obtain the modified expanded graphite. Mixing the modified expanded graphite and the polyvinylidene fluoride binder in a mass ratio of 1: 8-10, and stirring; and uniformly coating the mixture obtained after stirring on the surface of the passivated foam metal nickel titanium matrix nanotube, and drying to obtain the adsorbing material for removing rare metal ions in the wastewater. The invention has simple process and mild synthesis condition, and the prepared adsorbing material for removing rare metal ions in wastewater has large adsorption capacity and good recycling effect.
Description
Technical Field
The invention belongs to the technical field of materials for removing rare metal ions in wastewater. In particular to an adsorbing material for removing rare metal ions in wastewater and a preparation method thereof.
Background
In recent years, with the rapid development of socio-economic, the demand of rare metals is increasing, and at the same time, a large amount of waste water containing rare metal ions is discharged, and if the waste water is directly discharged into the environment, not only serious environmental problems are caused, but also the loss of rare metals is caused.
The existing synthetic materials for treating waste water containing rare metal ions can not meet the requirements of production and living conditions, for example, in the patent technology of 'a heavy metal waste water adsorbent and a preparation method thereof' (CN201910773358.0), although the adsorbent with high adsorption capacity to various heavy metals is prepared by mixing and calcining various raw materials, the preparation raw materials are various and the operation process is complex. For another example, the patent technology of "an inorganic porous material for removing heavy metals and preparation and application thereof" (CN201910539630.9) adopts humic acid to modify graphene oxide, and then intercalates the modified graphene oxide into montmorillonite sheets, so that the prepared adsorption material has low adsorption capacity although the raw materials are cheap and easy to obtain.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a preparation method of an adsorbing material for removing rare metal ions in wastewater, which is simple in process and mild in synthesis conditions.
In order to achieve the purpose, the invention adopts the technical scheme that:
step one, placing expanded graphite in mixed acid according to the concentration of 8-9 g/L, ultrasonically stirring for 3-5 h at room temperature, diluting with deionized water, carrying out solid-liquid separation, and washing to be neutral; and then drying for 2-4 h at 50-70 ℃ and under the vacuum degree of less than 200Pa to prepare the carboxylated expanded graphite.
Step two, mixing the carboxylated expanded graphite and the R-alkene-n-amine according to the mass ratio of 1: 40-60, and ultrasonically stirring for 20-40 min at room temperature; then carrying out open oil bath for 3-5 h in a fume hood at the temperature of 120-130 ℃, washing the oil bath to be neutral by using deionized water, and carrying out solid-liquid separation; and drying for 2-4 h at 50-70 ℃ and under the vacuum degree of less than 200Pa, and grinding until the particle size is 100-500 mu m to obtain the modified expanded graphite.
Mixing the modified expanded graphite and the polyvinylidene fluoride binder according to the mass ratio of 1: 8-10, and stirring for 3-5 minutes by using a magnetic stirrer; and (3) obtaining a mixture of the modified expanded graphite and polyvinylidene fluoride, uniformly coating the mixture on the surface of the passivated foam metal nickel titanium matrix skeleton nanotube, and drying for 12-13 h at 40-60 ℃ under the condition that the vacuum degree is less than 200Pa to obtain the adsorbing material for removing rare metal ions in the wastewater.
The synthetic method of the mixed acid comprises the following steps: 60-70% by mass of HNO3H with the mass fraction of 80-98%2SO4The volume ratio of (1) to (2.5-3.5), and the mass fraction of the HNO is 60-70%3And 80-98% of H by mass fraction2SO4Mixing to obtain mixed acid.
The preparation method of the passivated foam metal nickel titanium matrix skeleton nanotube comprises the following steps: firstly, washing the foam metal nickel titanium matrix nanotube for 3-5 times by using an acetone solution, washing the foam metal nickel titanium matrix nanotube to be neutral by using deionized water, then soaking the foam metal nickel titanium matrix nanotube in a nitric acid solution with the mass fraction of 60-70% for 5-10 min, washing the foam metal nickel titanium matrix nanotube to be neutral by using the deionized water, and baking the foam metal nickel titanium matrix nanotube until the surface turns yellow to obtain the passivated foam metal nickel titanium matrix nanotube.
The acetone solution was analytically pure.
The preparation method of the polyvinylidene fluoride binder comprises the following steps: firstly, drying polyvinylidene fluoride powder for 3-5 h at 50-70 ℃ and under the vacuum degree of less than 200Pa to obtain dried polyvinylidene fluoride powder; and then mixing the dried polyvinylidene fluoride powder with N-methyl pyrrolidone according to the mass ratio of the dried polyvinylidene fluoride powder to the N-methyl pyrrolidone of 1 to (15-25) to obtain the polyvinylidene fluoride binder.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
firstly, placing expanded graphite in mixed acid, ultrasonically stirring, washing and drying to prepare carboxylated expanded graphite; mixing the carboxylated expanded graphite with the R-alkene-n-amine, stirring, carrying out oil bath, washing, drying and grinding to obtain modified expanded graphite; and then mixing the modified expanded graphite with the polyvinylidene fluoride binder, stirring, uniformly coating on the surface of the passivated foam metal nickel titanium matrix nanotube, and drying to obtain the adsorbing material for removing rare metal ions in the wastewater. The invention has simple process, and the rest processes except the drying process are carried out at normal temperature and normal pressure, and the synthesis condition is mild.
The modification process of the invention increases the number of hydrophilic functional groups such as hydroxyl, carboxyl and the like on the surface of the expanded graphite, and the hydrophilic functional groups can react with a large number of amino and imino functional groups on the surface of R-alkene-n-amine to form stable modified expanded graphite. The modified expanded graphite retains the huge specific surface area and high-temperature resistance stability of the original expanded graphite, so that the modified expanded graphite retains the characteristic of large adsorption capacity, and the maximum adsorption capacity of the prepared adsorption material for removing rare metal ions in wastewater can reach 1000 mg/g-1The above.
According to the invention, the R-alkene-n-amine is successfully grafted on the surface of the carboxylated expanded graphite, so that the carboxylated expanded graphite has the capability of selectively adsorbing rare metals in wastewater, the adsorbed rare metal ions can be smoothly desorbed, and the removal rate of the rare metal ions is over 80 percent after the carboxylated expanded graphite is recycled for 6 times. Has wide application prospect in the aspect of removing and recovering rare metals.
Therefore, the invention has simple process and mild synthesis condition, and the prepared adsorbing material for removing the rare metal ions in the wastewater has large adsorption capacity and good recycling effect.
Drawings
FIG. 1 is a scanning electron micrograph of a modified expanded graphite prepared according to the present invention;
FIG. 2 is a photograph of an adsorbing material for removing rare metal ions from wastewater according to the present invention;
FIG. 3 is a partial enlarged nanotube structure view as indicated by the circled area shown in FIG. 2;
FIG. 4 is a graph showing the effect of recycling the adsorbent for removing rare metal ions from wastewater shown in FIG. 2.
Detailed Description
The invention is further described with reference to the following figures and detailed description, without limiting its scope.
In this embodiment:
the acetone solution is analytically pure:
the wastewater refers to industrial wastewater containing rare metal ions such as chromium, molybdenum, rhenium, osmium and the like.
The detailed description is omitted in the embodiments.
Example 1
An adsorbing material for removing rare metal ions in wastewater and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, according to the concentration of 8g/L, placing the expanded graphite in mixed acid, ultrasonically stirring for 3 hours at room temperature, diluting with deionized water, carrying out solid-liquid separation, and washing to be neutral; then drying for 2h at 50 ℃ and the vacuum degree of 110Pa to prepare the carboxylated expanded graphite.
Step two, mixing the carboxylated expanded graphite and the R-alkene-n-amine according to the mass ratio of 1: 40, and ultrasonically stirring for 20min at room temperature; then, opening an oil bath for 3 hours in a fume hood at the temperature of 120 ℃, washing the oil bath to be neutral by using deionized water, and carrying out solid-liquid separation; and drying for 2h at 50 ℃ and under the vacuum degree of 110Pa, and grinding until the particle size is more than or equal to 100 mu m and less than 300 mu m to obtain the modified expanded graphite.
Mixing the modified expanded graphite and the polyvinylidene fluoride binder according to the mass ratio of 1: 8, and stirring for 3 minutes by using a magnetic stirrer; obtaining a mixture of the modified expanded graphite and polyvinylidene fluoride, then uniformly coating the mixture on the surface of the passivated foam metal nickel titanium matrix nanotube, and drying for 12 hours at the temperature of 40 ℃ and the vacuum degree of 110Pa to prepare the adsorbing material for removing rare metal ions in the wastewater.
The synthetic method of the mixed acid comprises the following steps: 68% by mass of HNO3H with the mass fraction of 98%2SO4The volume ratio of (1) to (2.5) and the mass fraction of HNO is 68 percent3And said mass fraction is 98% of H2SO4Mixing to obtain mixed acid.
The preparation method of the passivated foam metal nickel titanium matrix skeleton nanotube comprises the following steps: firstly, washing the foam metal nickel titanium matrix nanotube for 3 times by using an acetone solution, washing the foam metal nickel titanium matrix nanotube to be neutral by using deionized water, then soaking the foam metal nickel titanium matrix nanotube in a nitric acid solution with the mass fraction of 60% for 5min, washing the foam metal nickel titanium matrix nanotube to be neutral by using the deionized water, and baking the foam metal nickel titanium matrix nanotube until the surface turns yellow to obtain the passivated foam metal nickel titanium matrix nanotube.
The preparation method of the polyvinylidene fluoride binder comprises the following steps: firstly, drying polyvinylidene fluoride powder for 3 hours at 50 ℃ under the vacuum degree of 110Pa to obtain dried polyvinylidene fluoride powder; and then mixing the dried polyvinylidene fluoride powder with N-methyl pyrrolidone according to the mass ratio of the dried polyvinylidene fluoride powder to the N-methyl pyrrolidone of 1: 15 to obtain the polyvinylidene fluoride binder.
In the R-ene-n-amine: r represents a substituent group, R is C4(ii) a n represents the number of amino groups, and n is 3.
The using method of the adsorbing material for removing rare metal ions in wastewater prepared in the embodiment is as follows:
with analytically pure grade K2OsO4The preparation concentration is 400 mg.L-1OsO of (1)4 2-100mL of the ion solution, the solution prepared in this example for removing rare metal ions from wastewaterAn adsorbent material is immersed in the OsO4 2-Placing the ionic solution in a constant-temperature magnetic stirrer for dynamic adsorption, and adsorbing at 25 deg.C and pH 4 for 40min to obtain solution with adsorption capacity of 426mg g-1。
After adsorption is finished, removing rare metal ions in the wastewater from the OsO by using an adsorbing material4 2-And taking out the ionic solution, wiping the surface moisture by using filter paper, immersing the ionic solution into 0.5mol/L HCl solution, ultrasonically leaching for 3 hours at room temperature, washing the ionic solution to be neutral by using deionized water, and drying the ionic solution to enable the adsorbing material to be reused.
Example 2
An adsorbing material for removing rare metal ions in wastewater and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, according to the concentration of 8.5g/L, placing the expanded graphite in mixed acid, ultrasonically stirring for 4 hours at room temperature, diluting with deionized water, carrying out solid-liquid separation, and washing to be neutral; then drying for 3h at the temperature of 60 ℃ and the vacuum degree of 150Pa to prepare the carboxylated expanded graphite.
Step two, mixing the carboxylated expanded graphite and the R-alkene-n-amine according to the mass ratio of 1: 50, and ultrasonically stirring for 30min at room temperature; then, the mixture is subjected to open oil bath for 4 hours in a fume hood at the temperature of 125 ℃, washed to be neutral by deionized water, and subjected to solid-liquid separation; and drying for 3h at 60 ℃ and under the vacuum degree of 150Pa, and grinding until the particle size is more than or equal to 300 mu m and less than 400 mu m to obtain the modified expanded graphite.
Mixing the modified expanded graphite and the polyvinylidene fluoride binder according to the mass ratio of the modified expanded graphite to the polyvinylidene fluoride binder of 1: 9, and stirring for 4 minutes by using a magnetic stirrer; then evenly coating the surface of the passivated foam metal nickel titanium matrix skeleton nanotube, and drying for 12.5 hours at the temperature of 50 ℃ and under the vacuum degree of 150Pa to prepare the adsorbing material for removing rare metal ions in the wastewater.
The synthetic method of the mixed acid comprises the following steps: 68% by mass of HNO3H with the mass fraction of 98%2SO4The volume ratio of (1) to (3) is 68 percent of HNO3And said mass fraction is 98% of H2SO4Mixing to obtain mixed acid.
The preparation method of the passivated foam metal nickel titanium matrix skeleton nanotube comprises the following steps: firstly, washing the foam metal nickel titanium matrix nanotube for 4 times by using an acetone solution, washing the foam metal nickel titanium matrix nanotube to be neutral by using deionized water, then soaking the foam metal nickel titanium matrix nanotube in a nitric acid solution with the mass fraction of 68% for 7.5min, washing the foam metal nickel titanium matrix nanotube to be neutral by using the deionized water, and baking the foam metal nickel titanium matrix nanotube until the surface turns yellow to obtain the passivated foam metal nickel titanium matrix nanotube.
The preparation method of the polyvinylidene fluoride binder comprises the following steps: firstly, drying polyvinylidene fluoride powder for 4 hours at the temperature of 60 ℃ and under the vacuum degree of 150Pa to obtain dried polyvinylidene fluoride powder; and then mixing the dried polyvinylidene fluoride powder with N-methyl pyrrolidone according to the mass ratio of the dried polyvinylidene fluoride powder to the N-methyl pyrrolidone of 1: 20 to obtain the polyvinylidene fluoride binder.
In the R-ene-n-amine: r represents a substituent group, R is C6(ii) a n represents the number of amino groups, and n is 4.
The using method of the adsorbing material for removing rare metal ions in wastewater prepared in the embodiment is as follows:
with analytically pure grade Na2ReO4The preparation concentration is 400 mg.L-1ReO of4 2-100mL of ionic solution (conductivity 220. mu.S cm at 25 ℃)-1) The set temperature was 25 ℃ and the solution pH was 4. The adsorbing material for removing rare metal ions in wastewater prepared in the embodiment is used as a positive electrode, an equiheavy foam metal nickel titanium base skeleton nanotube which is only subjected to passivation treatment is used as a negative electrode, the adsorbing material is parallelly inserted into a solution, the height of the water inlet area of the polar plates is kept consistent, the distance between the polar plates is 30mm, the voltage between the polar plates is 1.0V, the adsorption is completed in 40 minutes, and the adsorption capacity is 1090mg g.g-1。
And after adsorption is finished, the two polar plates are powered off and reversely connected, then the two polar plates are placed in 0.5mol/L HCl solution, ultrasonic leaching is carried out for 3 hours at room temperature, deionized water is used for washing until the two polar plates are neutral, drying is carried out, and the adsorbing material can be reused.
Example 3
An adsorbing material for removing rare metal ions in wastewater and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, according to the concentration of 9g/L, placing the expanded graphite in mixed acid, ultrasonically stirring for 5 hours at room temperature, diluting with deionized water, carrying out solid-liquid separation, and washing to be neutral; then drying for 4h at 70 ℃ and under the vacuum degree of 190Pa to prepare the carboxylated expanded graphite.
Step two, mixing the carboxylated expanded graphite and the R-alkene-n-amine according to the mass ratio of 1: 60, and ultrasonically stirring for 40min at room temperature; then, opening an oil bath for 5 hours in a fume hood at the temperature of 130 ℃, washing the oil bath to be neutral by using deionized water, and carrying out solid-liquid separation; and drying for 4h at 70 ℃ and under the vacuum degree of 190Pa, and grinding until the particle size is more than or equal to 400 mu m and less than 500 mu m to obtain the modified expanded graphite.
Mixing the modified expanded graphite and the polyvinylidene fluoride binder according to the mass ratio of the modified expanded graphite to the polyvinylidene fluoride binder of 1: 10, and stirring for 5 minutes by using a magnetic stirrer; and then uniformly coating the surface of the passivated foam metal nickel titanium matrix skeleton nanotube, and drying for 13 hours at the temperature of 60 ℃ and the vacuum degree of 190Pa to prepare the adsorbing material for removing rare metal ions in the wastewater.
The synthetic method of the mixed acid comprises the following steps: 68% by mass of HNO3H with the mass fraction of 98%2SO4The volume ratio of (1) to (3.5) and the mass fraction of HNO is 68 percent3And said mass fraction is 98% of H2SO4Mixing to obtain mixed acid.
The preparation method of the passivated foam metal nickel titanium matrix skeleton nanotube comprises the following steps: firstly, washing the foam metal nickel titanium matrix nanotube for 5 times by using an acetone solution, washing the foam metal nickel titanium matrix nanotube to be neutral by using deionized water, then soaking the foam metal nickel titanium matrix nanotube in a nitric acid solution with the mass fraction of 70% for 10min, washing the foam metal nickel titanium matrix nanotube to be neutral by using the deionized water, and baking the foam metal nickel titanium matrix nanotube until the surface turns yellow to obtain the passivated foam metal nickel titanium matrix nanotube.
The preparation method of the polyvinylidene fluoride binder comprises the following steps: firstly, drying polyvinylidene fluoride powder for 5 hours at 70 ℃ under the condition that the vacuum degree is 190Pa to obtain dried polyvinylidene fluoride powder; and then mixing the dried polyvinylidene fluoride powder with N-methyl pyrrolidone according to the mass ratio of the dried polyvinylidene fluoride powder to the N-methyl pyrrolidone of 1: 25 to obtain the polyvinylidene fluoride binder.
In the R-ene-n-amine: r represents a substituent group, R is C8(ii) a n represents the number of amino groups, and n is 5.
The using method of the adsorbing material for removing rare metal ions in wastewater prepared in the embodiment is as follows:
with analytically pure grade Na2ReO4The preparation concentration is 400 mg.L-1ReO of4 2-100mL of ionic solution (conductivity 220. mu.S cm at 25 ℃)-1) The set temperature was 25 ℃ and the solution pH was 4. The adsorbing material for removing rare metal ions in wastewater prepared in the example was used as a positive electrode, an equiheavy foam metal nickel titanium base skeleton nanotube which was only passivated was used as a negative electrode, and was inserted into the solution in parallel, the water inlet areas of the plates were kept consistent, the gap was 30mm, the voltage between the plates was 1.0V, the adsorption was completed in 40 minutes, and the adsorption capacity was 1076mg · g-1。
And after adsorption is finished, the two polar plates are powered off and reversely connected, then the two polar plates are placed in 0.5mol/L HCl solution, ultrasonic leaching is carried out for 3 hours at room temperature, deionized water is used for washing until the two polar plates are neutral, drying is carried out, and the adsorbing material can be reused.
The specific implementation mode and the prior art have the following positive effects:
firstly, placing the expanded graphite in mixed acid, ultrasonically stirring, washing and drying to prepare carboxylated expanded graphite; mixing the carboxylated expanded graphite with the R-alkene-n-amine, stirring, carrying out oil bath, washing, drying and grinding to obtain modified expanded graphite; and then mixing the modified expanded graphite with the polyvinylidene fluoride binder, stirring, uniformly coating on the surface of the passivated foam metal nickel titanium matrix nanotube, and drying to obtain the carbon nano material, namely the adsorption material for removing rare metal ions in the wastewater. The specific implementation mode has simple process, and the rest processes except the drying process are carried out at normal temperature and normal pressure, so the synthesis condition is mild.
The modification process of the embodiment increases the number of hydrophilic functional groups such as hydroxyl, carboxyl and the like on the surface of the expanded graphite, and can react with a large number of amino and imino functional groups on the surface of the R-alkene-n-amine to form the stable modified expanded graphite. The modified expanded graphite is shown in the attached drawing, fig. 1 is a scanning electron microscope image of the modified expanded graphite prepared in example 2, and it can be seen from fig. 1 that the modified expanded graphite retains rich pore structures of the expanded graphite and has the advantage of large specific surface area; FIG. 2 is a photograph of the adsorbing material for removing rare metal ions in wastewater prepared in example 2, and it can be seen from FIG. 2 that the modified expanded graphite has been successfully loaded on the surface of the foam metal nickel titanium matrix nanotube; FIG. 3 is a partial enlarged nanotube structure diagram marked by the circular area shown in FIG. 2. from FIG. 3, it can be seen that the large specific surface area of the foam metal nickel titanium matrix nanotube provides a large number of attachment sites for the expanded graphite. Therefore, the expanded graphite modified by the embodiment of the invention retains the huge specific surface area and high-temperature resistant stability of the original expanded graphite, so that the modified expanded graphite retains the characteristic of large adsorption capacity, and the maximum adsorption capacity of the prepared adsorbing material for removing rare metal ions in wastewater can reach 1000mg g-1The above.
In the present embodiment, since the R-ene-n-amine is successfully grafted onto the surface of the carboxylated expanded graphite, the carboxylated expanded graphite has the ability of selectively adsorbing the rare metals in the wastewater, as shown in fig. 4, the adsorbed rare metal ions can be smoothly desorbed, and fig. 4 is a graph of the regeneration efficiency of the cycle of the adsorbing material for removing the rare metal ions in the wastewater shown in fig. 2. As can be seen from fig. 4, although the regeneration efficiency of the adsorbent for removing rare metal ions in wastewater was gradually decreased, the removal rate of rare metal ions after 6 cycles was 80% or more, and it was found that the adsorbent had good recyclability. Therefore, the product prepared by the embodiment has wide application prospect in the aspects of removing rare metals in wastewater and recycling.
Therefore, the specific implementation method has simple process and mild synthesis conditions, and the prepared adsorbing material for removing the rare metal ions in the wastewater has large adsorption capacity and good recycling effect.
Claims (6)
1. A preparation method of an adsorbing material for removing rare metal ions in wastewater is characterized by comprising the following specific steps:
step one, placing expanded graphite in mixed acid according to the concentration of 8-9 g/L, ultrasonically stirring for 3-5 h at room temperature, diluting with deionized water, carrying out solid-liquid separation, and washing to be neutral; then drying for 2-4 h at 50-70 ℃ and under the vacuum degree of less than 200Pa to prepare carboxylated expanded graphite;
step two, mixing the carboxylated expanded graphite and the R-alkene-n-amine according to the mass ratio of 1: 40-60, and ultrasonically stirring for 20-40 min at room temperature; then carrying out open oil bath for 3-5 h in a fume hood at the temperature of 120-130 ℃, washing the oil bath to be neutral by using deionized water, and carrying out solid-liquid separation; drying for 2-4 h at 50-70 ℃ and under the vacuum degree of less than 200Pa, and grinding until the particle size is 100-500 mu m to obtain modified expanded graphite;
mixing the modified expanded graphite and the polyvinylidene fluoride binder according to the mass ratio of 1: 8-10, and stirring for 3-5 minutes by using a magnetic stirrer; and (3) obtaining a mixture of the modified expanded graphite and the polyvinylidene fluoride binder, then uniformly coating the mixture on the surface of the passivated foam metal nickel titanium matrix nanotube, and drying for 12-13 h at 40-60 ℃ under the condition that the vacuum degree is less than 200Pa to obtain the adsorbing material for removing rare metal ions in the wastewater.
2. The method according to claim 1 for removing rare materials from wastewaterThe preparation method of the adsorbing material for metal ions is characterized in that the synthesis method of the mixed acid comprises the following steps: 60-70% by mass of HNO3H with the mass fraction of 80-98%2SO4The volume ratio of (1) to (2.5-3.5), and the mass fraction of the HNO is 60-70%3And 80-98% of H by mass fraction2SO4Mixing to obtain mixed acid.
3. The method for preparing the adsorbing material for removing the rare metal ions in the wastewater according to claim 1, wherein the method for preparing the passivated foam metal nickel titanium matrix nanotube comprises the following steps: firstly, washing the foam metal nickel titanium matrix nanotube for 3-5 times by using an acetone solution, washing the foam metal nickel titanium matrix nanotube to be neutral by using deionized water, then soaking the foam metal nickel titanium matrix nanotube in a nitric acid solution with the mass fraction of 60-70% for 5-10 min, washing the foam metal nickel titanium matrix nanotube to be neutral by using the deionized water, and baking the foam metal nickel titanium matrix nanotube until the surface turns yellow to obtain a passivated foam metal nickel titanium matrix nanotube;
the acetone solution was analytically pure.
4. The method for preparing the adsorbing material for removing rare metal ions in wastewater according to claim 1, wherein the polyvinylidene fluoride binder is prepared by: firstly, drying polyvinylidene fluoride powder for 3-5 h at 50-70 ℃ and under the vacuum degree of less than 200Pa to obtain dried polyvinylidene fluoride powder; and then mixing the dried polyvinylidene fluoride powder with N-methyl pyrrolidone according to the mass ratio of the dried polyvinylidene fluoride powder to the N-methyl pyrrolidone of 1 to (15-25) to obtain the polyvinylidene fluoride binder.
5. The method for producing an adsorbing material for removing rare metal ions in wastewater according to claim 1, wherein in the R-en-n-amine: r represents a substituent group, R is C2、C4、C6… …, respectively; n represents the number of amino groups, and n is a natural number greater than zero.
6. An adsorbing material for removing rare metal ions in wastewater, which is characterized in that the adsorbing material for removing rare metal ions in wastewater is prepared according to the preparation method of the adsorbing material for removing rare metal ions in wastewater in any one of claims 1 to 5.
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| CN113371781A (en) * | 2021-06-16 | 2021-09-10 | 李远响 | Efficient adsorption type sewage treatment agent and preparation method thereof |
| CN113816509A (en) * | 2021-09-28 | 2021-12-21 | 石文建 | Method for adsorbing rare metal ions in aqueous solution by using calcium sulfate whiskers |
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