CN110918056A - Roasted hydrotalcite/magnetic nano onion carbon composite adsorption material and preparation method and application thereof - Google Patents
Roasted hydrotalcite/magnetic nano onion carbon composite adsorption material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of adsorption materials, and particularly relates to a roasted hydrotalcite/magnetic nano onion carbon composite adsorption material and a preparation method and application thereof. The preparation method of the roasted hydrotalcite/magnetic nano onion carbon composite adsorption material provided by the invention comprises the following steps: providing a salt solution comprising magnesium ions and aluminum ions; dropwise adding the salt solution and the alkaline solution into the magnetic nano onion carbon dispersion liquid, and carrying out hydrothermal reaction to obtain hydrotalcite/magnetic nano onion carbon; and roasting the hydrotalcite/magnetic nano onion carbon to obtain the roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material. The composite adsorption material prepared by the invention can effectively adsorb fluoride ions in water, and can be recovered from the water through a magnetic separation technology, so that the regeneration and the utilization are realized; in addition, the preparation method provided by the invention is simple, convenient and easy to operate, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of adsorption materials, and particularly relates to a roasted hydrotalcite/magnetic nano onion carbon composite adsorption material and a preparation method and application thereof.
Background
Fluorine (F), is one of elements widely distributed in nature and trace elements required by the human body. The fluorine intake of human body mainly comes from drinking water, but the excessive or insufficient fluorine intake of human body will cause some harm. The optimal mass concentration of fluoride in drinking water beneficial to human bodies is regulated by the world health organization to be 0.5-1.5 mg/L; according to the domestic drinking water sanitary standard (GB5749-2006), the mass concentration limit of fluoride in the drinking water is 1.0 mg/L. When F is present in the human body-When the concentration is lower than 0.4mg/L, dental caries can be caused; when the concentration is higher than 1.5-4 mg/L, dental fluorosis is caused; even more, if the concentration is higher than 4mg/L, fluorosis will develop. If the fluorine-containing raw material is not deeply treated in the preparation and processing processes, the fluorine-containing raw material and the three wastes can be generated and enter the environment, so that F in the water body is generated-The standard exceeding can reach 10-20 mg/L in high fluorine areas in China, so the problem of fluorine pollution, especially F in water, is solved-The problem of exceeding standard becomes a major task and subject to be solved urgently.
The adsorption method is favored by the students due to its advantages of low cost, simple operation, high efficiency and strong practicability. Adsorbents are the core of adsorption processes, and research on adsorption processes often focuses on adsorbents. The adsorbents commonly used for water treatment mainly include activated carbon, nanoparticles, clay minerals, biological wastes, agricultural solid wastes, and the like. Among them, Layered Double Hydroxides (LDHs) have attracted attention from the last 90 s, which are anionic clay-type nanomaterials in the form of pillared layers with exchangeable anions between the layers and can remove pollutants in water by means of ion exchange properties and the like. As the adsorbent, LDH has the characteristics of large specific surface area, easy preparation, low cost, excellent adsorption performance, easy regeneration and recycling and the like, can better remove pollutants, and solves the problem of water pollution. However, LDH is not easily separated from the solution after adsorption is completed, and there is a drawback that recovery is difficult.
Disclosure of Invention
The invention aims to provide a calcined hydrotalcite/magnetic nano onion carbon composite adsorption material and a preparation method and application thereof. The composite adsorption material prepared by the invention can effectively adsorb fluorine ions in water, and can be recovered from water by a magnetic separation technology, so that the regeneration and the utilization are realized.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a roasted hydrotalcite/magnetic nano onion carbon composite adsorption material, which comprises the following steps:
providing a salt solution comprising magnesium ions and aluminum ions;
dropwise adding the salt solution and the alkaline solution into the magnetic nano onion carbon dispersion liquid, and carrying out hydrothermal reaction to obtain hydrotalcite/magnetic nano onion carbon;
and roasting the hydrotalcite/magnetic nano onion carbon to obtain the roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material.
Preferably, the concentration of magnesium ions in the salt solution is 19-20 mmol/100mL, and the concentration of aluminum ions is 9-11 mmol/100 mL;
the alkaline solution is a mixed solution of sodium hydroxide and sodium carbonate or a mixed solution of sodium hydroxide and sodium bicarbonate; the pH value of the alkaline solution is 10-14.
Preferably, the molar ratio of the total amount of magnesium ions and aluminum ions in the salt solution to the sodium hydroxide in the alkaline solution is (28-31): (160-170).
Preferably, the concentration of the magnetic nano onion carbon dispersion liquid is 0.73-0.83 g/100 mL.
Preferably, the total dosage ratio of the magnetic nano onion carbon in the magnetic nano onion carbon dispersion liquid to the magnesium ions and the aluminum ions in the salt solution is (0.73-0.83) g: (28-31) mmol.
Preferably, when the salt solution and the alkaline solution are dripped into the magnetic nano onion carbon dispersion liquid, the pH value of the system is 9-10; the dropping speed of the salt solution is 2-10 mL/min; the dropping speed of the alkaline solution is 2-10 mL/min.
Preferably, the temperature of the hydrothermal reaction is 90-160 ℃, and the time is 3-6 h.
Preferably, the roasting temperature is 400-550 ℃ and the roasting time is 2-5 h.
The invention also provides a calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared by the preparation method in the technical scheme, and the calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material is of an amorphous flocculent structure.
The invention also provides application of the calcined hydrotalcite/magnetic nano onion carbon composite adsorption material in adsorption of fluorine ions in water.
The preparation method of the roasted hydrotalcite/magnetic nano onion carbon composite adsorption material provided by the invention comprises the following steps: providing a salt solution comprising magnesium ions and aluminum ions; dropwise adding the salt solution and the alkaline solution into the magnetic nano onion carbon dispersion liquid, and carrying out hydrothermal reaction to obtain hydrotalcite/magnetic nano onion carbon; and roasting the hydrotalcite/magnetic nano onion carbon to obtain the roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material. In the hydrothermal reaction process, a salt solution containing magnesium ions and aluminum ions and an alkaline solution are mixed, hydrotalcite is obtained by in-situ growth on the surface of magnetic nano onion carbon, after roasting, the layered structure of the hydrotalcite collapses, water molecules between layers of the hydrotalcite are removed, and CO between the layers is removed3 2-(from alkaline solution) also decompose to form CO2But the magnetic nano onion carbon is not affected in the roasting process, and finally the composite adsorbing material with the amorphous flocculent structure is obtained. The calcined hydrotalcite/magnetic nano onion carbon composite prepared by the inventionAfter the composite adsorbing material is roasted, the composite adsorbing material is substantially metal oxide, the interior of the composite adsorbing material is no longer in a laminated structure, and interlayer anions do not exist. In addition, the preparation method provided by the invention is simple, convenient and easy to operate, and is suitable for industrial production.
The invention also provides a calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared by the preparation method in the technical scheme, and the calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material is of an amorphous flocculent structure. The results of the examples show that the specific surface area of the composite adsorbing material provided by the invention is 104.95m2(ii)/g, total pore volume 0.32cm3The average pore diameter is 12.21nm, which shows that the composite adsorption material provided by the invention has large specific surface area and excellent adsorption performance, and can better remove fluorine ions in water; the composite adsorbing material provided by the invention has good superparamagnetism, and can be quickly separated from water under the action of an external magnetic field and recycled.
Drawings
FIG. 1 is an SEM image of a calcined hydrotalcite/magnetic nano-onion carbon composite adsorbing material prepared in example 1 of the present invention;
fig. 2 is an SEM image of hydrotalcite/magnetic nano onion carbon prepared in comparative example 1;
FIG. 3 is an XRD diagram of hydrotalcite, calcined hydrotalcite and calcined hydrotalcite/magnetic nano onion carbon composite adsorption material;
FIG. 4 shows N of the calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared in example 1 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 5 is a pore size distribution diagram of a calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared in example 1 of the present invention;
FIG. 6 is an FTIR spectrum of a calcined hydrotalcite/magnetic nano-onion carbon composite adsorbent material prepared in example 1 of the present invention;
FIG. 7 is a hysteresis loop diagram of a calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared in example 1 of the present invention;
FIG. 8 shows that the calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared in example 1 of the present invention adsorbs F-XRD pattern of the latter sample.
Detailed Description
The invention provides a preparation method of a roasted hydrotalcite/magnetic nano onion carbon composite adsorption material, which comprises the following steps:
providing a salt solution comprising magnesium ions and aluminum ions;
dropwise adding the salt solution and the alkaline solution into the magnetic nano onion carbon dispersion liquid, and carrying out hydrothermal reaction to obtain hydrotalcite/magnetic nano onion carbon;
and roasting the hydrotalcite/magnetic nano onion carbon to obtain the roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material.
The present invention provides a salt solution comprising magnesium ions and aluminum ions. In the invention, the concentration of magnesium ions in the salt solution is preferably 19-20 mmol/100mL, and more preferably 20mmol/100 mL. In the present invention, the agent providing the magnesium ion is preferably magnesium nitrate, and in the specific embodiment of the present invention, Mg (NO) is preferably used3)2·6H2O。
In the invention, the concentration of aluminum ions in the salt solution is preferably 9-11 mmol/100mL, and more preferably 10mmol/100 mL. In the present invention, the agent for providing the aluminum ion is preferably aluminum nitrate, and in the embodiment of the present invention, Al (NO) is preferably used3)3·9H2O。
The specific preparation method of the salt solution is not particularly limited in the present invention, and a preparation method well known in the art may be adopted.
In the present invention, the alkaline solution is preferably a mixed solution of sodium hydroxide and sodium carbonate, or a mixed solution of sodium hydroxide and sodium bicarbonate. In the invention, the pH value of the alkaline solution is preferably 10-14, and more preferably 11-12.5. In the invention, when the alkaline solution is a mixed solution of sodium hydroxide and sodium carbonate, the mass ratio of the sodium hydroxide to the sodium carbonate is preferably (6.5-6.8): (5.0-5.5), more preferably 6.75: 5.3; when the alkaline solution is a mixed solution of sodium hydroxide and sodium bicarbonate, the mass ratio of the sodium hydroxide to the sodium bicarbonate is preferably 1: (1.5-2.5), more preferably 1: 2.
In the invention, the molar ratio of the total amount of magnesium ions and aluminum ions in the salt solution to the sodium hydroxide in the alkaline solution is preferably (28-31): (160-170), more preferably 30 (168-169). The invention provides necessary alkaline environment for synthesizing the hydrotalcite by using the alkaline solution.
In the invention, the concentration of the magnetic nano onion carbon dispersion liquid is preferably 0.73-0.83 g/100mL, and more preferably 0.78g/100 mL; the total dosage ratio of the magnetic nano onion carbon in the magnetic nano onion carbon dispersion liquid to the magnesium ions and the aluminum ions in the salt solution is preferably (0.73-0.83) g: (28-31) mmol, more preferably 0.78 g: 30 mmol.
In the invention, when the salt solution and the alkaline solution are dripped into the magnetic nano onion carbon dispersion liquid, the pH value of the system is preferably kept at 9-10, and more preferably 10 all the time. In the invention, the dropping speed of the salt solution is preferably 2-10 mL/min, and more preferably 5-8 mL/min; the dropping speed of the alkaline solution is preferably 2-10 mL/min, and more preferably 3-6 mL/min. The salt solution and the alkaline solution are preferably simultaneously dripped into the magnetic nano onion carbon dispersion liquid, so that the hydrotalcite and the magnetic nano onion carbon are uniformly and tightly contacted. In the invention, the dropwise addition is preferably carried out under the condition of constant-temperature stirring, and the constant-temperature is preferably 70-90 ℃, and more preferably 80 ℃; the stirring speed is preferably 100-150 r/min, and more preferably 120 r/min. The effect of limiting the dropwise addition under the condition of constant-temperature stirring is uniform dispersion, and the bonding strength of the hydrotalcite and the magnetic nano onion carbon is favorably improved.
In the invention, the temperature of the hydrothermal reaction is preferably 90-160 ℃, and more preferably 100-120 ℃; the time is preferably 3 to 6 hours, and more preferably 3 to 4 hours. In the hydrothermal reaction process, magnesium ions, aluminum ions and an alkaline solution synthesize hydrotalcite on the surface of the magnetic nano onion carbon to obtain hydrotalcite/magnetic nano onion carbon.
According to the invention, after the hydrothermal reaction is finished, the obtained system is preferably cooled to room temperature, and then the obtained solid substance is sequentially washed, dried and ground to obtain the hydrotalcite/magnetic nano onion carbon. In the present invention, the washing detergent is preferably deionized water, and the number of washing times is not particularly limited in the present invention, and washing to neutrality is preferable. In the invention, the drying temperature is preferably 75-85 ℃, and more preferably 80 ℃; the drying time is preferably 10-14 h, and more preferably 12 h.
After obtaining the hydrotalcite/magnetic nano onion carbon, the invention roasts the hydrotalcite/magnetic nano onion carbon to obtain the roasted hydrotalcite/magnetic nano onion carbon composite adsorption material. In the invention, the roasting temperature is preferably 400-550 ℃, and more preferably 550 ℃; the roasting time is preferably 2-5 h, and more preferably 2 h. In the roasting process, the lamellar structure of the hydrotalcite/the magnetic nano onion carbon is destroyed, and the roasted hydrotalcite/the magnetic nano onion carbon composite adsorbing material with the amorphous flocculent structure is obtained.
The invention also provides a calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared by the preparation method in the technical scheme, and the calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material is of an amorphous flocculent structure. The specific surface area of the composite adsorbing material provided by the invention is preferably 95-120 m2(iv)/g, more preferably 104.95m2(ii)/g; the total pore volume is preferably 0.28-0.35 cm3G, more preferably 0.32cm3(ii)/g; the average pore diameter is preferably 10 to 15.5nm, and more preferably 12.21 nm.
The invention also provides application of the calcined hydrotalcite/magnetic nano onion carbon composite adsorption material in adsorption of fluorine ions in water. According to the invention, the roasted hydrotalcite/magnetic nano onion carbon composite adsorption material is preferably directly put into water for adsorbing and removing fluorine ions in the water. In the invention, when the concentration of the fluorine ions in the water is 10-100 mg/L, the adsorption rate is 2.17-49.87%, the adsorption amount is 4.98-33.22 mg/g, and the adsorption effect is excellent.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
5.12g Mg (NO)3)2·6H2O and 3.75gAl (NO)3)3·9H2Dissolving O in 100mL of deionized water, and stirring until the O is dissolved to obtain a salt solution; 6.75g NaOH and 5.30g Na2CO3Dissolving in 100mL of deionized water, and stirring until the solution is dissolved to obtain an alkali solution; 0.78g of magnetic nano onion carbon (MCNOs) is weighed into 100mL of deionized water, placing in ultrasonic cleaning machine (SB-5200DT, Ningbo Xinzhi Biotechnology Co., Ltd.) for ultrasonic treatment for 15min to obtain MCNOs dispersion, placing the MCNOs dispersion subjected to ultrasonic treatment in a heat collection type constant temperature heating magnetic stirrer (DF-101S, consolidated Co., Ltd.) at 80 deg.C, stirring, then dropwise adding the salt solution and the alkali solution into the MCNOs dispersion liquid through a peristaltic pump, keeping the pH of the solution at 9-10 in the dropwise adding process, wherein the dropping speed of the salt solution is 5mL/min, the dropping speed of the alkali solution is 8mL/min, after the dropping is finished, the solution is poured into a reaction kettle, placing in an electrothermal blowing dry box (DHG-9015A, Shanghai-Hengyun scientific instruments Co., Ltd.) at 100 deg.C for hydrothermal reaction for 4 h; cooling the reaction kettle to room temperature, taking out gray precipitate, washing with deionized water to neutrality, drying in an electrothermal blowing drying oven at 80 deg.C for 12 hr, and grinding to obtain hydrotalcite/magnetic nanometer onion carbon (LDH/MCNOs);
placing the LDH/MCNOs in a box type electric furnace (SX-G07103, Tianjin medium-ring electric furnace Co., Ltd.), and roasting at 550 ℃ for 2h to obtain a roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material (CLDH/MCNOs); the obtained CLDH/MCNOs had a specific surface area of 104.95m2(ii)/g, total pore volume 0.32cm3(ii)/g, average pore diameter 12.21 nm;
50mL of fluoride ion standard solution with the concentration of 100mg/L is put into a conical flask, 0.01g of CLDH/MCNOs is added, the conical flask is put into a cell crusher and is adsorbed for 60min under the conditions of the power of 180W and the constant temperature (298K), the adsorption rate is 6.62 percent, the adsorption quantity is 33.22mg/g, and the conical flask has excellent adsorption effect.
Example 2
5.12g Mg (NO)3)2·6H2O and 3.75gAl (NO)3)3·9H2Dissolving O in 100mL of deionized water, and stirring until the O is dissolved to obtain a salt solution; 6.75g NaOH and 5.30g Na2CO3Dissolving in 100mL of deionized water, and stirring until the solution is dissolved to obtain an alkali solution; 0.78g of magnetic nano onion carbon (MCNOs) is weighed into 100mL of deionized water, placing in ultrasonic cleaning machine (SB-5200DT, Ningbo Xinzhi Biotechnology Co., Ltd.) for ultrasonic treatment for 15min to obtain MCNOs dispersion, placing the MCNOs dispersion subjected to ultrasonic treatment in a heat collection type constant temperature heating magnetic stirrer (DF-101S, consolidated Co., Ltd.) at 80 deg.C, stirring, then dropwise adding the salt solution and the alkali solution into the MCNOs dispersion liquid through a peristaltic pump, keeping the pH of the solution at 9-10 in the dropwise adding process, wherein the dropping speed of the salt solution is 6mL/min, the dropping speed of the alkali solution is 6mL/min, after the dropping is finished, the solution is poured into a reaction kettle, placing in an electrothermal blowing dry box (DHG-9015A, Shanghai-Hengyun scientific instruments Co., Ltd.) at 100 deg.C for hydrothermal reaction for 4 h; cooling the reaction kettle to room temperature, taking out gray precipitate, washing with deionized water to neutrality, drying in an electrothermal blowing drying oven at 80 deg.C for 12 hr, and grinding to obtain hydrotalcite/magnetic nanometer onion carbon (LDH/MCNOs);
placing the LDH/MCNOs in a box type electric furnace (SX-G07103, Tianjin medium-ring electric furnace Co., Ltd.), and roasting at 400 ℃ for 5h to obtain a roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material (CLDH/MCNOs); the obtained CLDH/MCNOs had a specific surface area of 115m2(ii)/g, total pore volume 0.31cm3(ii)/g, average pore diameter of 13.2 nm;
50mL of fluoride ion standard solution with the concentration of 100mg/L is put into a conical flask, 0.01g of CLDH/MCNOs is added, the conical flask is put into a cell crusher and is adsorbed for 60min under the conditions of the power of 180W and the constant temperature (298K), the adsorption rate is 4.96 percent, the adsorption capacity is 24.92mg/g, and the conical flask has excellent adsorption effect.
Example 3
5.12g Mg (NO)3)2·6H2O and 3.75gAl (NO)3)3·9H2Dissolving O in 100mL of deionized water, and stirring until the O is dissolved to obtain a salt solution; 6.75g NaOH and 5.30g Na2CO3Dissolving in 100mL of deionized water, and stirring until the solution is dissolved to obtain an alkali solution; 0.78g of magnetic nano onion carbon (MCNOs) is weighed into 100mL of deionized water, placing in ultrasonic cleaning machine (SB-5200DT, Ningbo Xinzhi Biotechnology Co., Ltd.) for ultrasonic treatment for 15min to obtain MCNOs dispersion, placing the MCNOs dispersion subjected to ultrasonic treatment in a heat collection type constant temperature heating magnetic stirrer (DF-101S, consolidated Co., Ltd.) at 80 deg.C, stirring, then dropwise adding the salt solution and the alkali solution into the MCNOs dispersion liquid through a peristaltic pump, keeping the pH of the solution at 9-10 in the dropwise adding process, wherein the dropping speed of the salt solution is 4mL/min, the dropping speed of the alkali solution is 5mL/min, after the dropping is finished, the solution is poured into a reaction kettle, placing in an electrothermal blowing dry box (DHG-9015A, Shanghai-Hengyun scientific instruments Co., Ltd.) at 100 deg.C for hydrothermal reaction for 4 h; cooling the reaction kettle to room temperature, taking out gray precipitate, washing with deionized water to neutrality, drying in an electrothermal blowing drying oven at 80 deg.C for 12 hr, and grinding to obtain hydrotalcite/magnetic nanometer onion carbon (LDH/MCNOs);
placing the LDH/MCNOs in a box type electric furnace (SX-G07103, Tianjin medium-ring electric furnace Co., Ltd.), and roasting at 500 ℃ for 3h to obtain a roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material (CLDH/MCNOs); the obtained CLDH/MCNOs had a specific surface area of 120m2(ii)/g, total pore volume 0.32cm3(ii)/g, average pore diameter of 10.7 nm;
50mL of fluoride ion standard solution with the concentration of 100mg/L is put into a conical flask, 0.01g of CLDH/MCNOs is added, the conical flask is put into a cell crusher and is adsorbed for 60min under the conditions of the power of 180W and the constant temperature (298K), the adsorption rate is 5.63 percent, the adsorption quantity is 28.24mg/g, and the conical flask has excellent adsorption effect.
Example 4
5.12g Mg (NO)3)2·6H2O and 3.75gAl (NO)3)3·9H2Dissolving O in 100mL of deionized water, and stirring until the O is dissolved to obtain a salt solution; 6.75g NaOH and 5.30g Na2CO3Dissolving in 100mL of deionized water, and stirring until the solution is dissolved to obtain an alkali solution; 0.78g of magnetic nano onion carbon (MCNOs) is weighed into 100mL of deionized water, placing in ultrasonic cleaning machine (SB-5200DT, Ningbo Xinzhi Biotechnology Co., Ltd.) for ultrasonic treatment for 15min to obtain MCNOs dispersion, placing the MCNOs dispersion subjected to ultrasonic treatment in a heat collection type constant temperature heating magnetic stirrer (DF-101S, consolidated Co., Ltd.) at 80 deg.C, stirring, then dropwise adding the salt solution and the alkali solution into the MCNOs dispersion liquid through a peristaltic pump, keeping the pH of the solution at 9-10 in the dropwise adding process, wherein the dropping speed of the salt solution is 8mL/min, the dropping speed of the alkali solution is 10mL/min, after the dropping is finished, the solution is poured into a reaction kettle, placing in an electrothermal blowing dry box (DHG-9015A, Shanghai-Hengyun scientific instruments Co., Ltd.) at 100 deg.C for hydrothermal reaction for 4 h; cooling the reaction kettle to room temperature, taking out gray precipitate, washing with deionized water to neutrality, drying in an electrothermal blowing drying oven at 80 deg.C for 12 hr, and grinding to obtain hydrotalcite/magnetic nanometer onion carbon (LDH/MCNOs);
placing the LDH/MCNOs in a box type electric furnace (SX-G07103, Tianjin medium-ring electric furnace Co., Ltd.), and roasting at 550 ℃ for 3h to obtain a roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material (CLDH/MCNOs); the obtained CLDH/MCNOs had a specific surface area of 110m2(ii)/g, total pore volume 0.30cm3(ii)/g, average pore diameter 15.2 nm;
50mL of 10mg/L fluorine ion standard solution is put into a conical flask, 0.01g of CLDH/MCNOs is added, the conical flask is put into a cell crusher and is adsorbed for 60min under the conditions of 180W of power and constant temperature (298K), the adsorption rate is 49.87 percent, the adsorption quantity is 27.41mg/g, and the conical flask has excellent adsorption effect.
Example 5
5.12g Mg (NO)3)2·6H2O and 3.75gAl(NO3)3·9H2Dissolving O in 100mL of deionized water, and stirring until the O is dissolved to obtain a salt solution; 6.75g NaOH and 5.30g Na2CO3Dissolving in 100mL of deionized water, and stirring until the solution is dissolved to obtain an alkali solution; 0.78g of magnetic nano onion carbon (MCNOs) is weighed into 100mL of deionized water, placing in ultrasonic cleaning machine (SB-5200DT, Ningbo Xinzhi Biotechnology Co., Ltd.) for ultrasonic treatment for 15min to obtain MCNOs dispersion, placing the MCNOs dispersion subjected to ultrasonic treatment in a heat collection type constant temperature heating magnetic stirrer (DF-101S, consolidated Co., Ltd.) at 80 deg.C, stirring, then dropwise adding the salt solution and the alkali solution into the MCNOs dispersion liquid through a peristaltic pump, keeping the pH of the solution at 9-10 in the dropwise adding process, wherein the dropping speed of the salt solution is 6mL/min, the dropping speed of the alkali solution is 10mL/min, after the dropping is finished, the solution is poured into a reaction kettle, placing in an electrothermal blowing dry box (DHG-9015A, Shanghai-Hengyun scientific instruments Co., Ltd.) at 100 deg.C for hydrothermal reaction for 4 h; cooling the reaction kettle to room temperature, taking out gray precipitate, washing with deionized water to neutrality, drying in an electrothermal blowing drying oven at 80 deg.C for 12 hr, and grinding to obtain hydrotalcite/magnetic nanometer onion carbon (LDH/MCNOs);
placing the LDH/MCNOs in a box type electric furnace (SX-G07103, Tianjin medium-ring electric furnace Co., Ltd.), and roasting at 450 ℃ for 5h to obtain a roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material (CLDH/MCNOs); the obtained CLDH/MCNOs had a specific surface area of 98m2In terms of/g, total pore volume of 0.29cm3(ii)/g, average pore diameter 14.3 nm;
50mL of 10mg/L fluorine ion standard solution is put into a conical flask, 0.01g of CLDH/MCNOs is added, the conical flask is put into a cell crusher and is adsorbed for 60min under the conditions of 180W of power and constant temperature (298K), the adsorption rate is 34.76 percent, the adsorption quantity is 19.10mg/g, and the conical flask has excellent adsorption effect.
Comparative example 1
LDH/MCNOs prepared in example 1 were used as comparative example 1.
Comparative example 2
Hydrotalcite (LDH) is prepared by hydrothermal synthesis method, and production plantJingjiang city Jinggao plastic science and technology Limited, with a size of 0.7 μm and a specific surface area of 15m2/g。
Comparative example 3
And (2) roasting at 350-550 ℃ by adopting a hydrothermal synthesis method to obtain roasted hydrotalcite (CLDH), wherein the production factory is Jingjiang Guangsheng rubber and plastic material factory, and the size of the Cloud hydrotalcite is 1.5 mu m.
Test example 1
The SEM picture of CLDH/MCNOs prepared in example 1 is shown in FIG. 1, the SEM picture of LDH/MCNOs prepared in comparative example 1 is shown in FIG. 2, and it can be seen from FIGS. 1-2 that LDH/MCNOs are lamellar, while the lamellar structure in the layer of CLDH/MCNOs calcined at 550 ℃ is destroyed to present an amorphous flocculent structure.
Test example 2
The XRD patterns of the LDH prepared in comparative example 2, the CLDH prepared in comparative example 3 and the CLDH/MCNOs prepared in example 1 are shown in FIG. 3. from FIG. 3, it can be seen that typical characteristic peaks of LDH disappear after calcination, and characteristic peaks of metal oxide appear, indicating that the layered structure of LDH collapses after calcination, water molecules between layers are removed, and CO between layers is removed3 2-Decomposition also takes place to form CO2(ii) a In addition, there are still characteristic diffraction peaks of carbon in the CLDH/MCNOs spectrum, indicating that MCNOs are not affected when fired at 550 ℃.
Test example 3
N of CLDH/MCNOs prepared in example 12The adsorption-desorption isotherms are shown in FIG. 4, the pore size distribution is shown in FIG. 5, and it can be seen from FIGS. 4 to 5 that the specific surface area, the total pore volume and the average pore size are 104.95m respectively2/g、0.32cm3At/g and 12.21nm, as can be seen in FIG. 4, the adsorption isotherm for CLDH/MCNOs is type IV with a hysteresis loop of type H3, indicating the presence of mesoporous structure in the sample; in addition, the average pore size further indicates that it is a mesoporous material.
Test example 4
The FTIR spectrum of CLDH/MCNOs prepared in example 1 is shown in FIG. 6, and it can be seen from FIG. 6 that the wave number is 3448cm-1The hydroxyl stretching vibration peak still appears, which shows that the CLDH/MCNOs sample still exists after being roasted at 550 DEG CPart of the laminated hydroxyl groups and interlayer water molecules, namely the acting force between each atom in LDH/MCNOs and molecules is strong, so that the interlayer water molecules are not completely removed; and at 1406cm-1CO observed therein3 2-Asymmetric stretching vibration peak also indicates CO3 2-Not completely decomposed; and exists at 1052cm-1Has a weak peak of CO3 2-Symmetric telescopic peak due to CO3 2-Due to the influence of laminate hydroxyl and interlayer water molecules; furthermore, it appears at 668cm-1The weak peak is the composite metal oxide formed after the firing.
Test example 5
The hysteresis loop diagram of CLDH/MCNOs prepared in example 1 is shown in FIG. 7, the graph at the upper left corner of FIG. 7 is the graph of magnetic separation effect, and it can be seen from FIG. 7 that CLDH/MCNOs still have good superparamagnetism, and although the saturation magnetization is only 1.10emu/g, the CLDH/MCNOs can be rapidly separated from water under the action of an external magnetic field, which indicates that the roasted CLDH/MCNOs are adsorbents which can be recycled by the magnetic separation means.
Test example 6
CLDH/MCNOs adsorption F prepared in example 1-The XRD pattern of the latter sample is shown in FIG. 8, and it is clear from FIG. 8 that there is no unadsorbed F present-The former metal oxide peaks, but the typical characteristic peaks of LDH such as (003), (006), (012), (015), (018), (110) and (113) appear, and the peak shapes are narrow, sharp and regular; this indicates that the LDH layered structure collapsed by calcination adsorbs F-The LDH can be recovered through reconstruction and can be attributed to the self special structure memory effect of the LDH, namely the CLDH/MCNOs which are calcined at 550 ℃ are substantially metal oxides; the interior of the porous material is no longer in a layered structure, and interlayer anions do not exist, and F is adsorbed when the porous material adsorbs-F adsorbed to the inside thereof-It can act as an anion between its layers to restore its layered structure by memory effect, and thus, F in water-Are removed by adsorption.
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 (10)
1. The preparation method of the roasted hydrotalcite/magnetic nano onion carbon composite adsorption material is characterized by comprising the following steps of:
providing a salt solution comprising magnesium ions and aluminum ions;
dropwise adding the salt solution and the alkaline solution into the magnetic nano onion carbon dispersion liquid, and carrying out hydrothermal reaction to obtain hydrotalcite/magnetic nano onion carbon;
and roasting the hydrotalcite/magnetic nano onion carbon to obtain the roasted hydrotalcite/magnetic nano onion carbon composite adsorbing material.
2. The preparation method according to claim 1, wherein the concentration of magnesium ions in the salt solution is 19 to 20mmol/100mL, and the concentration of aluminum ions is 9 to 11mmol/100 mL;
the alkaline solution is a mixed solution of sodium hydroxide and sodium carbonate or a mixed solution of sodium hydroxide and sodium bicarbonate; the pH value of the alkaline solution is 10-14.
3. The preparation method according to claim 2, wherein the molar ratio of the total amount of magnesium ions and aluminum ions in the salt solution to the sodium hydroxide in the alkaline solution is (28-31): (160-170).
4. The preparation method of claim 1, wherein the concentration of the magnetic nano onion carbon dispersion is 0.73-0.83 g/100 mL.
5. The method according to claim 1 or 4, wherein the total amount of magnesium ions and aluminum ions in the magnetic nano onion carbon and the salt solution in the magnetic nano onion carbon dispersion is (0.73-0.83) g: (28-31) mmol.
6. The preparation method according to claim 1, wherein when the salt solution and the alkaline solution are added dropwise to the magnetic nano onion carbon dispersion, the pH value of the system is 9-10; the dropping speed of the salt solution is 2-10 mL/min; the dropping speed of the alkaline solution is 2-10 mL/min.
7. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction is 90-160 ℃ and the time is 3-6 h.
8. The preparation method of claim 1, wherein the roasting temperature is 400-550 ℃ and the roasting time is 2-5 h.
9. The calcined hydrotalcite/magnetic nano onion carbon composite adsorbing material prepared by the preparation method of any one of claims 1 to 8 is characterized by having an amorphous flocculent structure.
10. The use of the calcined hydrotalcite/magnetic nano onion carbon composite adsorbent material according to claim 9 for adsorbing fluorine ions in water.
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