CN108905972B - Heavy metal ion adsorbent and preparation method and application thereof - Google Patents
Heavy metal ion adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a heavy metal ion adsorbent and a preparation method and application thereof. The heavy metal ion adsorbent provided by the invention comprises a modified carbon material and zero-valent iron doped in the modified carbon material; the modified carbon material is a carbon material containing an oxygen-containing group including a carboxyl group and/or a hydroxyl group. The heavy metal ion adsorbent provided by the invention comprises zero-valent iron, wherein the zero-valent iron has magnetism, and the zero-valent iron can improve the adsorption effect on heavy metal ions through the magnetism in the process of adsorbing the heavy metal ions. In addition, in the present invention, the modified carbon material contains an oxygen-containing group including a carboxyl group and/or a hydroxyl group, and the adsorption effect on heavy metal ions can be mentioned by chemical ion exchange interaction between the oxygen-containing group and the heavy metal ions. The heavy metal ion adsorbent provided by the invention has a good adsorption effect on heavy metal ions, and can be recycled.
Description
Technical Field
The invention relates to the field of heavy metal pollutant treatment, and particularly relates to a heavy metal ion adsorbent and a preparation method and application thereof.
Background
Heavy metals are difficult to be degraded by microorganisms due to high toxicity and can be enriched through a food chain, so that the heavy metals become a difficult problem to be solved urgently in the field of water pollution. Wherein, the chromium is derived from waste water of metal processing, electroplating, leather and other industriesCopper and nickel, etc. have become major water pollution problems. Research shows that heavy metal ions in water mainly contain Cu2+、Ni2+And Cr3+And the like. Enrichment of excess Cu in organisms2+、Ni2+And Cr3+Plasma can cause inflammation, neurasthenia, systemic disorders, reduced fertility, teratogenicity, and mutagenicity.
At present, the treatment of heavy metal polluted wastewater mainly comprises an adsorption method, a chemical precipitation method, an ion exchange resin method, an electrochemical method, a membrane treatment method and the like. However, the above method has a low adsorption rate for heavy metal ions, and cannot satisfy the requirement for the adsorption rate for heavy metal ions.
Disclosure of Invention
The invention provides a heavy metal ion adsorbent, and a preparation method and application thereof.
The invention provides a heavy metal ion adsorbent, which comprises a modified carbon material, ferric oxide and zero-valent iron; the iron oxide is attached to the surface of the modified carbon material; the zero-valent iron is doped in the modified carbon material; the modified carbon material is a carbon material containing an oxygen-containing group including one or more of a carboxyl group, a hydroxyl group, and a carbonyl group.
Preferably, the molar ratio of carbon to oxygen in the heavy metal ion adsorbent is 100: 2-10.
The invention also provides a preparation method of the heavy metal ion adsorbent in the technical scheme, which comprises the following steps:
(1) mixing water-soluble iron salt and a carbon material in water to obtain a mixed solution;
(2) under the protection of nitrogen, dropwise adding sodium borohydride aqueous solution into the mixed solution obtained in the step (1) to perform reduction reaction, so as to obtain a modified carbon material doped with zero-valent iron;
(3) and (3) oxidizing the modified carbon material doped with zero-valent iron obtained in the step (2) by using air to obtain the heavy metal ion adsorbent.
Preferably, the mass ratio of the water-soluble iron salt to the carbon material in the step (1) is 1-10: 1-5; the carbon material includes graphene, carbon nanotubes, or activated carbon.
Preferably, the concentration of the sodium borohydride aqueous solution in the step (2) is 10-100 g/L; the dropping speed of the sodium borohydride aqueous solution is 10-20 mL/min.
Preferably, the time of the reduction reaction in the step (2) is 30-50 min; and the time of the reduction reaction is counted by dropping sodium borohydride aqueous solution from the beginning.
Preferably, the volume ratio of the mass of the modified carbon material doped with zero-valent iron in the step (3) to air is 1-5 g: 10-100 mL.
Preferably, the temperature of the oxidation reaction in the step (3) is 60-80 ℃.
Preferably, the time of the oxidation reaction in the step (3) is 30-60 min.
The invention also provides application of the heavy metal ion adsorbent in the technical scheme or the heavy metal ion adsorbent prepared by the preparation method in the technical scheme in adsorption of heavy metal ions, wherein the heavy metal ions comprise Cu2+、Ni2+、Cr3+、Co2+And Mn2+One or more of (a).
The invention provides a heavy metal ion adsorbent, which comprises a modified carbon material, ferric oxide and zero-valent iron; the iron oxide is attached to the surface of the modified carbon material; the zero-valent iron is doped in the modified carbon material; the modified carbon material is a carbon material containing an oxygen-containing group including one or more of a carboxyl group, a hydroxyl group, and a carbonyl group. In the invention, the zero-valent iron has magnetism, and the zero-valent iron can improve the adsorption effect on heavy metal ions through the magnetism in the process of adsorbing the heavy metal ions. In the invention, the iron oxide is attached to the surface of the modified carbon material, which is beneficial to protecting zero-valent iron from being oxidized, thereby effectively improving the adsorption effect of the zero-valent iron on heavy metal ions. In addition, in the present invention, the oxygen-containing group and the heavy metal ion are chemically ion-exchanged to improve the adsorption effect on the heavy metal ion. The results of the examples show that the invention isThe heavy metal ion adsorbent provided by the invention has a high adsorption effect on heavy metal ions, and the heavy metal ion adsorbent provided by the invention has a high effect on Cu2+The adsorption amount of (B) is 30.2-65.1 mg/g, and the adsorption amount to Cu is2+The adsorption rate of the adsorbent is 30.2-65.1%; to Ni2+The adsorption amount of (A) is 26.4-31.4 mg/g, to Ni2+The adsorption rate of the adsorbent is 58.6-69.8%; for Cr3+The adsorption amount of (B) is 12.9-14.5 mg/g.
Moreover, the heavy metal ion adsorbent provided by the invention can simultaneously adsorb various heavy metal ions in pollutants due to the magnetism of the heavy metal ion adsorbent and the electrostatic interaction with the heavy metal ions, and has a good adsorption effect on each heavy metal ion. In addition, the heavy metal ion adsorbent provided by the invention can be recycled, and the recycling and regenerating performance is kept above 95% after 5 times of recycling.
Drawings
FIG. 1 is an electron microscope scanning image of the heavy metal ion adsorbent prepared in example 1 of the present invention;
FIG. 2 shows the heavy metal ion adsorbent pair Cr prepared in example 1 of the present invention3+Cycle curve of adsorption performance;
FIG. 3 is a FT-IR spectrum of the heavy metal ion adsorbent prepared in example 1 of the present invention.
Detailed Description
The invention provides a heavy metal ion adsorbent, which comprises a modified carbon material, ferric oxide and zero-valent iron; the iron oxide is attached to the surface of the modified carbon material; the zero-valent iron is doped in the modified carbon material; the modified carbon material is a carbon material containing an oxygen-containing group including one or more of a carboxyl group, a hydroxyl group, and a carbonyl group.
The heavy metal ion adsorbent provided by the invention comprises a modified carbon material; the modified carbon material is a carbon material containing an oxygen-containing group. In the invention, the oxygen-containing group is connected to the surface of the carbon material, and the molar ratio of carbon element to oxygen element in the heavy metal ion adsorbent is preferably 100: 2-10, more preferably 100: 4-8, and even more preferably 100: 5-7. In the invention, the surface of the modified carbon material contains oxygen-containing groups, and when heavy metal ions are adsorbed, electrostatic interaction exists between the oxygen-containing groups and the heavy metal ions, so that the adsorption effect of the heavy metal ion adsorbent on the heavy metal ions is improved. Taking heavy metal ions as copper ions as an example. The interaction between copper ions and oxygen-containing groups on the surface of the modified carbon material is shown as formula I or formula II:
the above reaction shows that Cu is due to electrostatic interaction2+And (4) chemically adsorbing on the surface of the modified carbon material. In addition, the iron oxide in the heavy metal ion adsorbent also provides an oxidized surface to adsorb heavy metal ions.
In the present invention, the carbon material preferably includes graphene, carbon nanotubes, or activated carbon. In the present invention, the source of graphene, carbon nanotube and activated carbon is not particularly limited, and commercially available products may be used.
The heavy metal ion adsorbent provided by the invention comprises iron oxide, wherein the iron oxide is attached to the surface of the modified carbon material, and the iron oxide is favorable for protecting zero-valent iron from being further oxidized and improving the adsorption effect of the zero-valent iron on heavy metal ions. In the present invention, the mass ratio of the iron oxide to the modified carbon material is preferably 0.05 to 0.15:1, more preferably 0.08 to 0.12:1, and still more preferably 0.1: 1.
The heavy metal ion adsorbent provided by the invention comprises zero-valent iron, wherein the zero-valent iron is doped in the modified carbon material. In the present invention, the mass ratio of the zero-valent iron to the modified carbon material is preferably 4.5 to 5.5:2.5 to 3.5, and more preferably 5: 3.
The invention provides a preparation method of a heavy metal ion adsorbent, which comprises the following steps:
(1) mixing water-soluble iron salt and a carbon material in water to obtain a mixed solution;
(2) under the protection of nitrogen, dropwise adding sodium borohydride aqueous solution into the mixed solution obtained in the step (1) to perform reduction reaction, so as to obtain a modified carbon material doped with zero-valent iron;
(3) and (3) oxidizing the modified carbon material doped with zero-valent iron obtained in the step (2) by using air to obtain the heavy metal ion adsorbent.
According to the invention, water-soluble iron salt and a carbon material are mixed in water to obtain a mixed solution.
In the present invention, the water-soluble iron salt preferably comprises one or more of ferric chloride, ferrous chloride, ferric sulfate or ferrous sulfate.
In the present invention, the mass ratio of the water-soluble iron salt to the carbon material is preferably 1-10: 1-5, more preferably 2-8: 2-4, and even more preferably 4-6: 2.5-3.5. According to the invention, the mass ratio of the water-soluble iron salt to the carbon material is preferably controlled within the above range, so that the subsequently obtained zero-valent iron can be fully doped in the carbon material, and the adsorption effect on heavy metal ions is improved.
In the present invention, the volume ratio of the total mass of the water-soluble iron salt and the carbon material to water is preferably 2 to 15g:100mL, and more preferably 5 to 10g:100 mL. The invention preferably controls the volume ratio of the total mass of the water-soluble ferric salt and the carbon material to the water within the range, so that the water-soluble ferric salt and the carbon material keep proper concentration, and the water-soluble ferric salt and the carbon material are favorably and fully reacted in the subsequent process.
The present invention does not require any particular embodiment of mixing the water-soluble iron salt and the carbon material, and the mixing method known to those skilled in the art may be used.
After the mixed solution is obtained, dropwise adding a sodium borohydride aqueous solution into the mixed solution for reduction reaction under the protection of nitrogen to obtain the modified carbon material doped with zero-valent iron.
The invention preferably leads the reduction reaction to be carried out under the protection of nitrogen by continuously introducing nitrogen. In the present invention, the flow rate of the nitrogen gas is preferably 100 to 500mL/min, more preferably 200 to 400mL/min, and even more preferably 250 to 35 mL/min. The invention preferably controls the flow of the nitrogen within the range, which is beneficial to the reduction reaction under the protection of the nitrogen; the invention carries out reduction reaction under the protection of the nitrogen, and is beneficial to reducing ferric iron to obtain zero-valent iron.
The invention adds sodium borohydride water solution into the mixed solution to carry out reduction reaction.
In the invention, the concentration of the sodium borohydride aqueous solution is preferably 10-100 g/L, more preferably 20-80 g/L, and even more preferably 40-60 g/L. The concentration of the sodium borohydride aqueous solution is preferably controlled within the range, so that the sodium borohydride can keep proper concentration, and the sodium borohydride can be favorably and fully reacted with the water-soluble iron salt.
In the present invention, the volume ratio of the sodium borohydride aqueous solution to the water-soluble iron salt is preferably 0.5 to 1.5:1.5 to 2.5, and more preferably 1: 2. The volume ratio of the sodium borohydride aqueous solution to the water-soluble ferric salt is preferably controlled within the range, so that the sodium borohydride and the ferric salt can fully react, and ferric iron can be reduced to zero-valent iron.
In the invention, the dropping speed of the sodium borohydride aqueous solution is preferably 10-20 mL/min, more preferably 12-18 mL/min, and more preferably 14-16 mL/min; the dropping temperature is preferably 50-70 ℃, more preferably 55-65 ℃, and more preferably 60 ℃, and the dropping temperature refers to the temperature of the sodium borohydride aqueous solution. According to the invention, sodium borohydride is mixed with the mixed solution in a manner of dropwise adding sodium borohydride into the mixed solution, so that the excessive violent reaction and the nonuniform reaction caused by the too high activity of the sodium borohydride are avoided, and the reaction can be smoothly carried out. In the invention, the sodium borohydride reacts with the iron salt/carbon material after contacting, and the sodium borohydride has strong reducibility and can reduce ferric iron in the iron salt/carbon material into zero-valent iron.
In addition, in the present invention, the carbon material is reacted with nitrogen and sodium borohydride to produce a modified carbon material. In the present invention, the surface of the modified carbon material contains oxygen-containing groups including one or more of hydroxyl groups, carboxyl groups, and carbonyl groups. When the heavy metal ions are adsorbed, the oxygen-containing groups and the heavy metal ions are interacted through chemical ion exchange, so that the aim of adsorbing the heavy metal ions is fulfilled.
In the invention, the temperature of the reduction reaction is preferably 50-70 ℃, more preferably 55-65 ℃, and more preferably 60 ℃, and the time of the reduction reaction is preferably 40-50 min, and more preferably 45 min. In the present invention, the time of the reduction reaction is preferably measured from the start of dropwise addition of the aqueous solution of sodium borohydride.
The invention reduces iron salt to zero-valent iron through reduction reaction. In the invention, the zero-valent iron has magnetism, and in the process of adsorbing heavy metal ions, the zero-valent iron is beneficial to improving the adsorption effect on the heavy metal ions through the magnetism of the zero-valent iron. Meanwhile, in the reduction reaction process, the carbon material reacts to generate the modified carbon material.
After the reduction reaction is finished, the invention preferably carries out filtration, filter cake drying and cooling treatment on the product of the reduction reaction in sequence under the protection of nitrogen to obtain the modified carbon material doped with zero-valent iron with stable performance.
The invention preferably carries out filtration treatment under the protection of nitrogen, which is beneficial to avoiding the oxidation of the reduced zero-valent iron. The present invention does not require any particular embodiment of filtration, and filtration means well known to those skilled in the art may be used.
According to the invention, the filter cake is preferably dried under the protection of nitrogen to obtain a dried reaction product. In the invention, the temperature of the drying treatment is preferably 60-80 ℃, and more preferably 65-75 ℃; the drying time is preferably 6-24 hours, and more preferably 10-20 hours. The invention preferably carries out drying treatment under the protection of nitrogen, which is beneficial to avoiding the oxidation of the reduced zero-valent iron.
According to the invention, the reaction product after drying treatment is preferably cooled to obtain the zero-valent iron doped modified carbon material with stable performance.
The embodiment of the cooling treatment in the present invention is not particularly limited, and a cooling treatment method known to those skilled in the art may be used.
The invention preferably adopts cooling treatment to stabilize the performance of the zero-valent iron doped in the carbon material, thereby being beneficial to obtaining the modified carbon material doped with the zero-valent iron with stable performance.
After the modified carbon material doped with zero-valent iron is obtained, the modified carbon material doped with zero-valent iron is oxidized by air to obtain the heavy metal ion adsorbent.
According to the invention, air is preferably injected into the modified carbon material doped with zero-valent iron to perform oxidation reaction. In the invention, the filling speed of the air is preferably 10-100 mL/min, more preferably 20-80 mL/min, and even more preferably 40-60 mL/min.
In the present invention, the air is preferably gaseous air; the volume ratio of the mass of the zero-valent iron-doped modified carbon material to air is 1-5 g: 10-100 mL, more preferably 2-4 g: 20-80 mL, and still more preferably 2.5-3.5 g: 40-60 mL. In the present invention, the air can oxidize the zero-valent iron on the surface of the modified carbon material to produce iron oxide. In the invention, the iron oxide on the surface of the modified carbon material is beneficial to protecting zero-valent iron in the modified carbon material from being oxidized, thereby being beneficial to ensuring the adsorption effect of the zero-valent iron on heavy metal ions.
In the invention, after the air is contacted with the modified carbon material doped with zero-valent iron, an oxidation reaction occurs to oxidize the zero-valent iron on the surface of the modified carbon material into iron oxide, so that an iron oxide film is formed on the surface of the modified carbon material, and the iron oxide film is favorable for protecting the zero-valent iron in the modified carbon material from being oxidized.
In the invention, the temperature of the oxidation reaction is preferably 60-80 ℃, more preferably 65-75 ℃, more preferably 70 ℃, and the time of the oxidation reaction is preferably 30-50 min, more preferably 35-45 min, more preferably 40 min.
After the oxidation reaction is finished, the invention preferably carries out cooling treatment on the oxidation reaction product to obtain the heavy metal ion adsorbent. In the present invention, the cooling method is preferably natural cooling.
The invention also provides the application of the heavy metal ion adsorbent in the technical scheme in adsorbing heavy metal ions, wherein the heavy metal ions comprise Cu2+、Ni2+、Cr3+、Co2+And Mn2+One or more of (a).
In the invention, the concentration of the heavy metal ions in the pollutants to be treated is preferably 50-150 mg/L.
In the invention, the mass ratio of the heavy metal ion adsorbent to the concentration of the pollutant to be treated is preferably 1g: 50-150 mg/L.
The invention has no specific requirements on the application mode of the heavy metal ion adsorbent in adsorbing heavy metal ions, and the application mode known by the technical personnel in the field can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Preparation of the heavy metal ion adsorbent: 1.14 grams of sodium borohydride was dissolved in 100ml of deionized water to form a sodium borohydride solution, and at the same time, another beaker containing 100ml of deionized water was taken and 2.7 grams of ferric chloride and 1 gram of graphene were added to form a ferric chloride/graphene solution. Then 100ml of ferric chloride/graphene solution is poured into a three-neck flask, nitrogen is continuously introduced, the hydrogen flow is 250ml/min, nitrogen is continuously introduced, and 100ml of sodium borohydride solution is slowly dripped into the three-neck flask at the dripping speed of 10 ml/min. After the completion of the dropping of the solution, the three-necked flask was sealed and placed in a glove box, the solution was filtered in the glove box to obtain a solid powder, and then the solid powder was placed in the flask and sealed and placed in a vacuum drying oven into which nitrogen gas had been previously introduced, followed by vacuum-pumping and drying at 60 ℃ for 12 hours. And after drying is finished, dropwise adding 20ml of air into the drying oven, then continuously keeping the sealing state of the drying oven, and taking out the solid powder after the temperature of the drying oven is reduced to room temperature to obtain the heavy metal ion adsorbent.
The heavy metal ion adsorbent obtained in the embodiment 1 comprises zero-valent iron, iron oxide and modified graphene; the modified graphene is graphene containing carboxyl, hydroxyl and carbonyl, the zero-valent iron is doped in the modified graphene, and the iron oxide is attached to the surface of the modified graphene; the mass ratio of the zero-valent iron to the modified graphene is 5:3, and the mass ratio of the iron oxide to the modified graphene is 0.1: 1.
Scanning electron microscope detection is carried out on the heavy metal ion adsorbent obtained in example 1, and the result is shown in fig. 1; in fig. 1, light gray represents activated carbon, dark black dots represent zero-valent iron, and as can be seen from fig. 1, the zero-valent iron is uniformly embedded into the activated carbon, which shows that the zero-valent iron and the activated carbon are well compounded, and the zero-valent iron is not easy to fall off, thereby being beneficial to the exertion of the magnetic adsorption performance and the improvement of the recycling performance.
The heavy metal ion adsorbent obtained in example 1 was subjected to an FT-IR test, and the test result is shown in fig. 3, and an FT-IR spectrum shows that characteristic peaks such as — OH, C ═ O, C-O exist on the surface of the adsorbent, indicating that the surface of the adsorbent is functionalized by oxygen-containing groups such as hydroxyl, carboxyl and carbonyl groups, and has high chemical activity.
Example 2
Preparation of the heavy metal ion adsorbent: 2.28 grams of sodium borohydride was dissolved in 100ml of deionized water to form a sodium borohydride solution, and at the same time, another beaker containing 100ml of deionized water was taken and 3.6 grams of ferric chloride and 1.5 grams of activated carbon were added to form a ferric chloride/activated carbon solution. Then 100ml of ferric chloride/activated carbon solution is poured into the three-neck flask, nitrogen is continuously introduced, the hydrogen flow is 150ml/min, nitrogen is continuously introduced, and 100ml of sodium borohydride solution is slowly dripped into the three-neck flask at the dripping speed of 10 ml/min. After the completion of the dropping of the solution, the three-necked flask was sealed and placed in a glove box, the solution was filtered in the glove box to obtain a solid powder, and then the solid powder was placed in the flask and sealed and placed in a vacuum drying oven into which nitrogen gas had been previously introduced, followed by vacuum-pumping and drying at 60 ℃ for 24 hours. And after drying is finished, dropwise adding 50ml of air into the drying oven, then continuously keeping the sealing state of the drying oven, and taking out the solid powder after the temperature of the drying oven is reduced to room temperature to obtain the heavy metal ion adsorbent.
The heavy metal ion adsorbent obtained in example 2 comprises zero-valent iron, iron oxide and modified activated carbon; the modified activated carbon is activated carbon containing carboxyl, hydroxyl and carbonyl, the zero-valent iron is doped in the modified activated carbon, and the iron oxide is attached to the surface of the modified activated carbon; wherein the mass ratio of the zero-valent iron to the modified activated carbon is 4.5:2.5, and the mass ratio of the iron oxide to the modified activated carbon is 0.15: 1.
Example 3
The experiment was performed according to the protocol of example 2, except that activated carbon was replaced with graphene.
Example 4
An experiment was performed according to the protocol of example 2, except that activated carbon was replaced with carbon nanotubes.
Example 5
Preparation of the heavy metal ion adsorbent: 5.35 grams of sodium borohydride was dissolved in 100ml of deionized water to form a sodium borohydride solution, and at the same time, another beaker containing 100ml of deionized water was taken and 5.7 grams of ferric chloride and 3.6 grams of activated carbon were added to form a ferric chloride/activated carbon solution. Then 100ml of ferric chloride/activated carbon solution is poured into the three-neck flask, nitrogen is continuously introduced, the hydrogen flow is 350ml/min, nitrogen is continuously introduced, and 100ml of sodium borohydride solution is slowly dripped into the three-neck flask at the dripping speed of 20 ml/min. After the completion of the dropping of the solution, the three-necked flask was sealed and placed in a glove box, the solution was filtered in the glove box to obtain a solid powder, and then the solid powder was placed in the flask and sealed and placed in a vacuum drying oven into which nitrogen gas had been previously introduced, followed by vacuum-pumping and drying at 80 ℃ for 6 hours. And after the drying is finished, dropping 100ml of air into the drying oven, continuously keeping the sealing state of the drying oven, and taking out the solid powder after the temperature of the drying oven is reduced to the room temperature to obtain the low-valence metal ion magnetic adsorbent. Adding the low-valence metal ion magnetic adsorbent into a methyl trioctyl ammonium chloride solution, slowly stirring for 1 hour, wherein the mass ratio of the adsorbent to the methyl trioctyl ammonium chloride solution is 5/1, then putting the mixed solution into a vacuum drying oven, and drying for 10 hours at 80 ℃ in a vacuum environment to obtain the heavy metal ion adsorbent.
The heavy metal ion adsorbent obtained in example 5 comprises zero-valent iron, iron oxide and modified activated carbon; the modified activated carbon is activated carbon containing carboxyl, hydroxyl and carbonyl, the zero-valent iron is doped in the modified activated carbon, and the iron oxide is attached to the surface of the modified activated carbon; wherein the mass ratio of the zero-valent iron to the modified activated carbon is 5.0:3.0, and the mass ratio of the iron oxide to the modified activated carbon is 0.05: 1.
Example 6
An experiment was performed according to the protocol of example 5, except that the activated carbon in example 5 was replaced with graphene.
Application example 1
The heavy metal ion adsorbent prepared in example 1 was subjected to adsorption performance test, and 1g of the heavy metal ion adsorbent prepared in example 1 was added to 1L of a heavy metal ion adsorbent containing 90mg/L Cr3+Testing the heavy metal ion adsorbent to Cr after stirring the polluted wastewater for 30 minutes3+Cr in polluted wastewater3+The adsorption effect of (1). The test results are shown in table 1.
Table 1 example 1 heavy metal ion adsorbent vs Cr3+Adsorption effect of
| For Cr3+Adsorption amount of (2) | For Cr in wastewater3+Adsorption rate of (2) | |
| Example 1 heavy Metal ion adsorbent | 14.5mg/g | 16.1％ |
As can be seen from the test results in Table 1, the present invention providesHeavy metal ion adsorbent of (2) to Cr3+The adsorption capacity of the heavy metal ion adsorbent is 14.5mg/g, and the heavy metal ion adsorbent provided by the invention can be used for adsorbing Cr in wastewater3+The adsorption rate of (D) was 16.1%. In the present invention, the amount of adsorbed Cr is3+Mass ratio of (d) to mass of the heavy metal ion adsorbent; adsorption rate of Cr adsorbed by adsorbent3+Quality of (2) and Cr in wastewater3+The mass ratio of (a).
Cr adsorption of heavy Metal ion adsorbent prepared in example 13+And (4) carrying out cycle test on the performance, and testing the cycle performance of the heavy metal ion adsorbent. The method for the cycle test comprises the following steps: adopt strong magnetic material such as neodymium iron boron magnet to inhale the adsorbent magnetism after the adsorbent uses, carry out the desorption processing of adsorbent afterwards, form highly concentrated heavy metal solution and adsorbent deposit after the desorption processing, can use once more after collecting the drying with the adsorbent deposit.
The test result of the cycle performance is shown in fig. 2, and it can be known from the test result of fig. 2 that the heavy metal ion adsorbent provided by the invention adsorbs Cr3+In the experiment, after the heavy metal ion adsorbent is recycled for 5 times, the recovery and regeneration performance of the heavy metal ion adsorbent is still kept above 95%.
Application example 2
The heavy metal ion adsorbents prepared in examples 2 to 4 were tested for adsorption performance, and 5mL of the heavy metal ion adsorbents prepared in examples 2 to 4 containing 100mg/L of Cu were added to 5mg of each heavy metal ion adsorbent2+Testing the heavy metal ion adsorbent to Cu after stirring the polluted wastewater for 30 minutes2+Cu in polluted wastewater2+The adsorption effect of (1). The test results are shown in table 2.
TABLE 2 examples 2-4 heavy metal ion adsorbent vs Cu2+Adsorption effect of
| For Cu2+Adsorption amount of (2) | For Cu in wastewater2+Adsorption rate of (2) | |
| Example 2 heavy Metal ion adsorbent | 48.6mg/g | 48.6％ |
| Example 3 heavy Metal ion adsorbent | 65.1mg/g | 65.1％ |
| Example 4 heavy Metal ion adsorbent | 30.2mg/g | 30.2％ |
As shown in the test results in Table 2, the heavy metal ion adsorbent provided by the invention has the advantages of high Cu content2+The adsorption capacity of the heavy metal ion adsorbent is 30.2-65.1 mg/g, and the heavy metal ion adsorbent provided by the invention can be used for adsorbing Cu in wastewater2+The adsorption rate of (A) is 30.2 to 65.1%.
Application example 3
The heavy metal ion adsorbents prepared in examples 5 to 6 were tested for adsorption performance, and 10mg of the heavy metal ion adsorbents prepared in examples 5 to 6 were added to 5mL of the heavy metal ion adsorbents containing 90mg/LNi2+And 50mg/L Cr3+After stirring the polluted wastewater for 30 minutes, testing the Ni of the heavy metal ion adsorbent2+And Cr3+The adsorption effect of (1). The test results are shown in table 3.
TABLE 3 examples 5-6 heavy metal ion adsorbent vs Ni2+And Cr3+Adsorption effect of
| To Ni2+Adsorption amount of (2) | To Ni2+Adsorption rate of (2) | For Cr3+Adsorption amount of (2) | For Cr3+Adsorption rate of (2) | |
| Example 5 | 26.4mg/g | 58.6％ | 12.9mg/g | 51.6％ |
| Example 6 | 31.4mg/g | 69.8％ | 14.3mg/g | 57.2％ |
As can be seen from the test results in Table 3, the heavy metal ion adsorbent provided by the invention can simultaneously adsorb Ni in wastewater2+And Cr3+Moreover, the heavy metal ion adsorbent provided by the invention is used for adsorbing Ni in wastewater2+And Cr3+Has high adsorption capacity and adsorption rate to Ni2+The adsorption amount of (B) is 26.4-31.4 mg/g, and the adsorption amount to Cr is3+The adsorption amount of (B) is 12.9-14.3 mg/g, and the adsorption amount to Ni2+The adsorption rate of the metal is 58.6-69.8%, and the metal is Cr3+The adsorption rate of (B) is 51.6 to 57.2%.
In conclusion, this documentThe heavy metal ion adsorbent provided by the invention can effectively adsorb Cu in pollutants2+、Ni2+And Cr3+The heavy metal ion adsorbent provided by the invention is used for adsorbing Cu2+The adsorption amount of (B) is 30.2-65.1 mg/g, and the adsorption amount to Cu is2+The adsorption rate of the adsorbent is 30.2-65.1%; to Ni2+The adsorption amount of (A) is 26.4-31.4 mg/g, to Ni2+The adsorption rate of the adsorbent is 58.6-69.8%; for Cr3+The adsorption amount of (B) is 12.9-14.5 mg/g. Moreover, the heavy metal ion adsorbent provided by the invention can simultaneously adsorb multiple heavy metals in pollutants, and has a good adsorption effect on each heavy metal. In addition, the heavy metal ion adsorbent provided by the invention can be recycled, and after 5 times of recycling, the recovery and regeneration performance is 95%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A heavy metal ion adsorbent comprises a modified carbon material, ferric oxide and zero-valent iron; the iron oxide is attached to the surface of the modified carbon material; the zero-valent iron is doped in the modified carbon material; the modified carbon material is a carbon material containing oxygen-containing groups, wherein the oxygen-containing groups comprise one or more of carboxyl, hydroxyl and carbonyl;
the preparation method of the heavy metal ion adsorbent comprises the following steps:
(1) mixing water-soluble iron salt and a carbon material in water to obtain a mixed solution;
(2) under the protection of nitrogen, dropwise adding sodium borohydride aqueous solution into the mixed solution obtained in the step (1) to perform reduction reaction, so as to obtain a modified carbon material doped with zero-valent iron;
(3) oxidizing the modified carbon material doped with zero-valent iron obtained in the step (2) by using air to obtain a heavy metal ion adsorbent; the volume ratio of the mass of the zero-valent iron-doped modified carbon material to air is 1-5 g: 10-100 mL; the temperature of the oxidation reaction is 60-80 ℃, and the time of the oxidation reaction is 30-60 min.
2. The heavy metal ion adsorbent according to claim 1, wherein a molar ratio of carbon to oxygen in the heavy metal ion adsorbent is 100: 2-10.
3. A method for producing the heavy metal ion adsorbent according to claim 1 or 2, comprising the steps of:
(1) mixing water-soluble iron salt and a carbon material in water to obtain a mixed solution;
(2) under the protection of nitrogen, dropwise adding sodium borohydride aqueous solution into the mixed solution obtained in the step (1) to perform reduction reaction, so as to obtain a modified carbon material doped with zero-valent iron;
(3) oxidizing the modified carbon material doped with zero-valent iron obtained in the step (2) by using air to obtain a heavy metal ion adsorbent; the volume ratio of the mass of the zero-valent iron-doped modified carbon material to air is 1-5 g: 10-100 mL; the temperature of the oxidation reaction is 60-80 ℃, and the time of the oxidation reaction is 30-60 min.
4. The preparation method according to claim 3, wherein the mass ratio of the water-soluble iron salt to the carbon material in the step (1) is 1-10: 1-5; the carbon material includes graphene, carbon nanotubes, or activated carbon.
5. The preparation method according to claim 3, wherein the concentration of the aqueous solution of sodium borohydride in the step (2) is 10-100 g/L; the dropping speed of the sodium borohydride aqueous solution is 10-20 mL/min.
6. The method according to any one of claims 3 to 5, wherein the time for the reduction reaction in the step (2) is 30 to 50 min; and the time of the reduction reaction is counted by dropping sodium borohydride aqueous solution from the beginning.
7. Use of the heavy metal ion adsorbent of claim 1 or 2 or the heavy metal ion adsorbent prepared by the preparation method of any one of claims 3 to 6 in adsorption of heavy metal ions, wherein the heavy metal ions comprise Cu2+、Ni2+、Cr3 +、Co2+And Mn2+One or more of (a).
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