CN110404507B - Zinc-aluminum hydrotalcite/carbon nanotube composite adsorption material, preparation method thereof and application thereof in gallium recovery - Google Patents
Zinc-aluminum hydrotalcite/carbon nanotube composite adsorption material, preparation method thereof and application thereof in gallium recovery Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a zinc-aluminum hydrotalcite carbon nanotube composite adsorption material and a preparation method and application thereof. The preparation method comprises the following steps: adding carbon nanotubes into a three-neck round-bottom flask filled with concentrated nitric acid and concentrated sulfuric acid, stirring in an ultrasonic water bath for reaction for 1.5h, cooling to room temperature, performing suction filtration and washing, and drying to obtain an intermediate product named as CNT-COOH; weighing zinc chloride and aluminum chloride hexahydrate in a beaker, adding deionized water, stirring until the deionized water is dissolved, adding the intermediate product obtained in the step 1), and slowly dropwise adding 2mol L of the intermediate product at a certain speed‑1Adjusting the pH value of the NaOH solution to 10, stirring for 2-5h, and then carrying out hydrothermal reaction to obtain a target product, namely Zn/Al-LDH @ CNTs. The method has the advantages of low synthesis cost, simple synthesis method, energy conservation, environmental protection, large adsorption capacity, high adsorption speed, wide application and practical applicability.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a zinc-aluminum hydrotalcite/carbon nanotube composite adsorption material as well as a preparation method and application thereof.
Background
Gallium is distributed in nature in a relatively dispersed manner, mainly exists in bauxite and zinc-soil ores, and has no independently-mined ore body, so that the amount of resources which can be developed and recycled at present is very small. At present, gallium is mainly recovered from acid alkaline immersion liquids such as aluminum-smelting zinc-smelting slag, gallium arsenide sludge, red mud, alunite, diode waste products, fly ash and the like. Gallium is a very valuable element, is originally used in the field of metallurgy, is now widely applied to various high-tech fields, such as the field of environmental remediation, uses the chemical, thermal and photocatalytic properties of gallium oxide as an alpha-gallium mixed oxide to degrade active blue, and in the field of medicine, the prepared gallium-containing compound can effectively and selectively resist cancer, and can be used as a glass material, a solar cell, a crystal, a thin film, a functional material, a catalyst and the like in the fields of nonlinear optics, optoelectronic devices, photovoltaics and the like. Therefore, the problem of gallium separation and enrichment has attracted attention, and the development of effective gallium-adsorbing materials has become a hot spot of current research.
The existing gallium adsorption method mainly comprises the following steps: precipitation electrolysis, reduction smelting extraction, resin adsorption, alkali fusion, etc. The most prominent defects of the methods are that the operation is complicated, the energy consumption is large and secondary pollution is easily caused when the low-concentration metal wastewater is treated. The functionalized material adsorption method is a more effective method for treating the metal-containing wastewater at present, and particularly has obvious advantages for treating low-concentration wastewater.
The Carbon Nanotubes (CNTs) are used as a novel adsorption material due to large specific surface, more pore structures, higher specific surface area, stability and excellent adsorption performance, and become an adsorbent and a carrier of pollutants in the environment. The carbon nano tube can effectively adsorb on dye due to the conjugated effect of the pi-pi electrons per se, and a large number of active sites can be generated by the carbon nano tube after oxidation, loading or modification, so that the adsorption capacity on metal is greatly improved.
Hydrotalcite materials belong to anionic layered compounds. The layered compound is a compound with a layered structure, interlayer ions and interchangeability, and some functional object substances are introduced into interlayer gaps and the interlayer distance is spread by utilizing the intercalation property of a layered compound main body under the action of strong polar molecules and the interchangeability of the interlayer ions so as to form the layered compound. The hydrotalcite material has the excellent performances of wide source, radiation resistance, strong thermal stability and the like, and is selected as an effective adsorbent to be applied to the field of metal recovery, but the single hydrotalcite material is easy to disperse and has an unstable structure.
Based on the above knowledge, there is no report on the absorption of rare earth elements by the zinc-aluminum hydrotalcite carbon nanotube.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to overcome the defect of unstable structure of hydrotalcite, and selects carbon nanotubes as structural support to be modified for absorbing gallium. The method has the advantages of simple operation method, abundant resources and low cost. The prepared composite material adsorbent has large adsorption capacity to gallium, is widely applicable and has practical applicability.
The invention is realized by the following technical scheme: a zinc-aluminum hydrotalcite/carbon nanotube composite adsorption material is prepared by the following steps:
1) adding carbon nano tubes into a three-neck round-bottom flask filled with concentrated nitric acid and concentrated sulfuric acid, carrying out ultrasonic water bath stirring reaction, cooling to room temperature, carrying out suction filtration and washing, and drying to obtain carboxylated carbon nano tubes named as CNT-COOH;
2) putting zinc chloride and aluminum chloride hexahydrate into a beaker, adding deionized water, stirring until the deionized water is dissolved, adding the carboxylated carbon nanotube obtained in the step 1), and slowly dripping 2mol L of the carboxylated carbon nanotube-1Adjusting the pH value of the NaOH solution to 10, stirring for 2-5h, then carrying out hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing and drying to obtain a target product Zn/Al-LDH @ CNTs.
Preferably, in the above zinc-aluminum hydrotalcite carbon nanotube composite adsorbing material, in step 1), the volume ratio of concentrated nitric acid: 1:1-5 of concentrated sulfuric acid; the concentration of the concentrated nitric acid is 16mol/L, and the concentration of the concentrated sulfuric acid is 18.4 mol/L.
Preferably, in the above zinc-aluminum hydrotalcite carbon nanotube composite adsorbing material, in step 1), the carbon nanotubes: the total volume of the concentrated nitric acid and the concentrated sulfuric acid is 1 g: 100-200 mL.
Preferably, in the step 1), the temperature of the ultrasonic water bath stirring reaction is 40-60 ℃, and the reaction time is 1-3 h.
Preferably, in the above-mentioned zinc-aluminum hydrotalcite carbon nanotube composite adsorbing material, in step 2), the molar ratio of zinc chloride: 1-5:1 of aluminum chloride hexahydrate; according to mass ratio, carboxylic carbon nano tube: zinc chloride ═ 1 g: 15.64g to 27.20 g.
Preferably, in the step 2), the hydrothermal reaction temperature is 90-130 ℃, and the reaction time is 20-28 h.
The application of the zinc-aluminum hydrotalcite carbon nanotube composite adsorption material in the recovery of rare earth metals is provided.
Preferably, for the above-mentioned application, said rare earth metal is gallium.
Preferably, the above application is carried out by adjusting the concentration of the gallium solution to 20-30 mg.L-1The zinc-aluminum hydrotalcite carbon nanotube composite adsorbing material as defined in claim 1 is added and oscillated for 20-28h at the temperature of 293-313K and the oscillation rate of 180 r/min.
Preferably, the application comprises the following steps of according to the solid-to-liquid ratio: gallium solution ═ 5-20 g: 1L of the compound.
The invention has the beneficial effects that:
1. the zinc-aluminum hydrotalcite/carbon nanotube composite material (Zn/Al-LDH @ CNTs) adsorbent prepared by the invention has high adsorption efficiency, and can efficiently and quickly adsorb gallium. The method disclosed by the invention is energy-saving and environment-friendly, large in adsorption capacity, high in adsorption speed, wide in application and practical in application.
2. The raw materials are rich: the hydrotalcite material is prepared by mixing two salt solutions according to a certain proportion to prepare an alkaline solution, and drying after coprecipitation and hydrothermal synthesis. The raw materials are convenient to obtain, the cost is low, and the method is suitable for industrial application.
3. The synthesis is simple: according to the invention, the carbon nano tube is subjected to carboxylation treatment and then is compounded with the zinc-aluminum hydrotalcite to prepare the adsorbent through hydrothermal reaction, so that the adsorbent has a good separation and enrichment effect on rare earth metal gallium.
4. No pollution: the solvent used in the method is all non-organic solvent, and the waste liquid is simply neutralized without polluting the environment.
5. The efficiency is high: the adsorbent prepared by the method has larger adsorption capacity to gallium in the waste liquid, can reach 314.43g/kg, and has high-efficiency adsorption.
6. The speed is high, and the adsorbent prepared by the method can reach 314.43g kg at the temperature of 303K and the oscillation speed of 180r/min-1When the concentration of gallium ions is 20mg/L, the adsorption balance can be achieved within 5 minutes, and the adsorption rate can reach more than 95 percent, so that the quick adsorption is realized.
In conclusion, the zinc-aluminum hydrotalcite/carbon nanotube composite material (Zn/Al-LDH @ CNTs) adsorbent prepared by the invention can effectively adsorb gallium ions. The adsorbent is rich in raw materials, simple to synthesize, energy-saving and environment-friendly, and has high adsorption efficiency, high speed and practical practicability.
Drawings
FIG. 1 is a schematic synthesis of Zn/Al-LDH @ CNTs prepared in example 1.
FIG. 2 is an infrared spectrum of Zn/Al-LDH @ CNTs adsorbent prepared in example 1 and CNT.
FIG. 3 is a graph of the effect of Zn/Al-LDH @ CNTs adsorbent prepared in example 2 on the adsorption of gallium at various acidity levels.
FIG. 4 is an adsorption isotherm plot of the Zn/Al-LDH @ CNTs adsorbent prepared in example 3 adsorbing gallium.
FIG. 5 is the effect of the adsorption shaking time of Zn/Al-LDH @ CNTs adsorbent prepared in example 4 on the gallium adsorption rate.
Detailed Description
The carbon nanotube used in the invention has an outer diameter of 20-30nm, a length of 0.5-2 μm and a purity of more than 98%.
EXAMPLE 1 preparation of Zinc-aluminum hydrotalcite/carbon nanotube composite Material
1. Preparation of zinc-aluminum hydrotalcite/carbon nano tube composite material
1) Carbon nanotubes (0.5g) were dispersed in a 250mL three-necked flask containing concentrated nitric acid (20mL) having a concentration of 16mol/L and concentrated sulfuric acid (60mL) having a concentration of 18.4 mol/L. Ultrasonically stirring for 1.5h in an ultrasonic water bath kettle at the temperature of 40 ℃. And after the solution is cooled to room temperature, diluting the concentrated acid solution, performing suction filtration and washing to obtain a carboxylated carbon nanotube, and drying in an oven at 50 ℃ to obtain an intermediate product, namely CNT-COOH.
2) The dried carboxylated carbon nanotubes (0.40g), aluminum chloride hexahydrate (0.02mol, 4.83g) and zinc chloride (0.06mol, 8.18g) were dissolved in 25mL of water. Slowly dripping 2mol L of the solution into the solution at a certain speed-1Adjusting the pH value of the NaOH solution to 10, stirring for 3h, transferring to a polytetrafluoroethylene liner reaction kettle, and carrying out hydrothermal reaction at 110 ℃ for 24 h.
3) After the hydrothermal reaction is finished, fully cooling the solution to room temperature, carrying out suction filtration, washing with water for 3 times, and drying in a 50 ℃ oven to obtain the target product Zn/Al-LDH @ CNTs, wherein the preparation process is shown in figure 1.
2. Characterization of Zinc-aluminum hydrotalcite/carbon nanotube composite Material
The prepared Zn/Al-LDH @ CNTs and carbon nano tubes are subjected to infrared spectrum detection, and as can be seen from figure 2, the concentration of the Zn/Al-LDH @ CNTs and the carbon nano tubes is 3420cm-1The nearby peak should be the stretching vibration characteristic peak of-OH, thereby indicating that the material has a large amount of-OH. At 1420cm-1Around and 830cm-1Nearby should be CO3 2-Characteristic peak of (2). 780cm-1Near and 560cm-1The vicinity is the characteristic peak of the metal oxide. Thus, Zn/Al-LDH @ CNTs are successfully prepared.
Example 2 adsorption effect of Zn-Al hydrotalcite/carbon nanotube composite adsorbent on gallium at different acidity
10mg of the Zn/Al-LDH @ CNTs composite material prepared in the example 1 is respectively added into 10mL of gallium solution with the concentration of 20mg/L and the pH value of 1, 2, 3, 8 and 10, then the gallium solution is put into a shaking box with the rotating speed of 180r/min and the temperature of 303K to be shaken for 24 hours, the filtration is carried out, the concentration of the filtrate and the stock solution is measured, and the adsorption rate is calculated.
As shown in fig. 3, the adsorption result of the zinc-aluminum hydrotalcite/carbon nanotube composite adsorbent showed a maximum adsorption rate of 96% or more for gallium at pH 3. This may be due to the hydrogen ions in the phenolic hydroxyl groups and Ga (OH)2+And Ga (OH)2 +A cation exchange takes place with the aim of adsorbing Ga (III), and Ga (OH)2+And Ga (OH)2 +In the form mainly existing at pH 3. As the pH value increases, gallium ions exist in the form of anions Ga (OH)4 -And Ga (OH)5 2-. For the strong acid condition, the hydrogen ion in the solution and the hydrogen in the phenolic hydroxyl are in Ga (OH)2+And Ga (OH)2 +The adsorption forms competition, which is not favorable for the adsorption of gallium.
Example 3 adsorption Capacity of Zinc-aluminum hydrotalcite/carbon nanotube composite adsorbent to gallium
10mg of the Zn/Al-LDH @ CNTs composite material prepared in example 1 is weighed, added into Ga (III) solution with different concentrations under the condition of pH 3, shaken for 24h at the temperature of 303K, and after filtration, the concentrations of the stock solution and the filtrate are determined.
The isothermal curve is shown in fig. 4, and it can be seen from fig. 4 that the adsorption isotherm type is Langmuir type, and the adsorption slope is gradually decreased with the increase of concentration until the adsorption equilibrium is reached, which conforms to the characteristic of chemisorption. The maximum adsorption capacity of the adsorbent Zn/Al-LDH @ CNTs to Ga (III) is 314.43mg g at the solution pH value of 3 of Ga (III)-1。
Example 4 influence of adsorption shock time of Zinc-aluminum hydrotalcite/carbon nanotube composite adsorbent
10mg of the Zn/Al-LDH @ CNTs composite material prepared in example 1 was weighed and added to 10mL of a 20 mg. L solution-1The gallium solution with the pH value of 3 is vibrated for 5min, 10min, 20min, 30min, 1h, 2h and 4h respectively under the conditions that the temperature is 303K and the vibration speed is 180r/min, and the change of the adsorption amount of the Zn/Al-LDH @ CNTs to Ga (III) along with time is researched.
As a result, as shown in FIG. 5, the amount of Ga (III) adsorbed by the Zn/Al-LDH @ CNTs adsorbent was in equilibrium at 5min, and the adsorption rate was about 96% at equilibrium.
Example 5 selection of resolver for Zinc-aluminum hydrotalcite/carbon nanotube composite adsorbent
150mg of the Zn/Al-LDH @ CNTs adsorbent prepared in example 1 was weighed out and added to 150mL of 20mg L-1And (3) shaking the gallium solution with the pH value of 3 for 2 hours, taking out the gallium solution, filtering the gallium solution, and drying the composite material which is adsorbed and saturated.
And (3) mixing the dried composite material with eluents with different concentrations in a solid-to-liquid ratio of 1:1, shaking for 12h, taking out and filtering, and measuring the concentration of gallium ions in the solution, wherein the results are shown in table 1.
As can be seen from Table 1, 1.0mol L-1The elution effect of NaOH on the gallium-loaded composite material is the best, and can reach 99.4%. But 0.8mol L-1The elution effect of NaOH on the gallium-loaded composite material is 99.1%, and the elution effects of the eluents with two concentrations are not greatly different, so that the requirements can be met. From the viewpoint of environmental protection, a low concentration of eluent (0.8mol L) was selected- 1NaOH) is more suitable.
TABLE 1 elution rates of different eluents for gallium
Claims (7)
1. The application of the zinc-aluminum hydrotalcite/carbon nano tube composite adsorbing material in the recovery of the gallium ions is characterized in that the concentration of the gallium solution is adjusted to be 20-30 mg.L-1Adding a zinc-aluminum hydrotalcite carbon nanotube composite adsorption material, and oscillating for 20-28h at the temperature of 293-313K and the oscillation rate of 180 r/min;
the preparation method of the zinc-aluminum hydrotalcite/carbon nanotube composite adsorption material comprises the following steps:
adding carbon nano tubes into a three-neck round-bottom flask filled with concentrated nitric acid and concentrated sulfuric acid, carrying out ultrasonic water bath stirring reaction, cooling to room temperature, carrying out suction filtration and washing, and drying to obtain carboxylated carbon nano tubes named as CNT-COOH;
putting zinc chloride and aluminum chloride hexahydrate into a beaker, adding deionized water, stirring until the deionized water is dissolved, adding the carboxylated carbon nanotube obtained in the step 1), and slowly dripping 2mol L of the carboxylated carbon nanotube-1Adjusting the pH value of the NaOH solution to 10, stirring for 2-5h, then carrying out hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing and drying to obtain a target product Zn/Al-LDH @ CNTs.
2. The use according to claim 1, characterized in that in step 1), the ratio by volume of concentrated nitric acid: concentrated sulfuric acid =1: 1-5; the concentration of the concentrated nitric acid is 16mol/L, and the concentration of the concentrated sulfuric acid is 18.4 mol/L.
3. The use according to claim 1, wherein in step 1), the carbon nanotubes have a mass ratio of carbon nanotubes to liquid nanotubes in terms of solid-to-liquid ratio: the total volume of the concentrated nitric acid and the concentrated sulfuric acid is 1 g: 100-200 mL.
4. The use of claim 1, wherein in the step 1), the temperature of the ultrasonic water bath stirring reaction is 40-60 ℃, and the reaction time is 1-3 h.
5. The use according to claim 1, wherein in step 2), the molar ratio of zinc chloride: aluminum chloride hexahydrate =1-5: 1; according to mass ratio, carboxylic carbon nano tube: zinc chloride =1 g: 15.64g to 27.20 g.
6. The use according to claim 1, wherein in step 2), the hydrothermal reaction is carried out at a temperature of 90-130 ℃ for a reaction time of 20-28 h.
7. The use of claim 1, wherein the zinc-aluminum hydrotalcite carbon nanotube composite adsorbent material comprises, in solid to liquid ratio: gallium solution =5-20 g: 1L of the compound.
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