CN112691641B - Hydroxyl-modified tremella three-dimensional carbon nano sheet, preparation method thereof and application thereof in gallium recovery - Google Patents
Hydroxyl-modified tremella three-dimensional carbon nano sheet, preparation method thereof and application thereof in gallium recovery Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of effective recycling materials of gallium, and particularly relates to a hydroxyl-modified tremella-shaped three-dimensional carbon nano sheet material, a preparation method thereof and application thereof in recycling of gallium. The technical scheme adopted is as follows: the tremella three-dimensional carbon nano sheet matrix is obtained by directly carbonizing sodium citrate serving as a carbon source, and titanium dioxide and sorbitol which are rich in hydroxyl groups are selected to be chemically bonded with the matrix. The preparation method is quick, simple and convenient, the reaction condition is mild, the environment is free of pollution, the prepared composite material can not only improve the hydrophilicity and the regenerability of the carbon material and solve the problem that titanium dioxide is difficult to recycle in aqueous solution as an adsorbent, but also increase the functional groups on the surface of the adsorbent, namely active sites, so that the adsorption performance on scattered gallium ions is effectively improved, and the preparation method has practical applicability.
Description
Technical Field
The invention belongs to the technical field of preparation of effective recycling materials of gallium, and particularly relates to a tremella three-dimensional carbon nano-sheet matrix which is obtained by carbonizing sodium citrate at high temperature, wherein the matrix is rich in carboxyl and hydroxyl, butyl titanate and sorbitol are compounded on the matrix, and the synthesized hydroxyl-modified tremella three-dimensional carbon nano-sheet aims at effectively adsorbing gallium from a solution containing metal ion gallium.
Background
The main existence forms of the gallium are associated minerals, such as vanadium titano-magnetite, sphalerite, lead zinc ore, coal fly ash and the like, and the industrially produced gallium mainly comes from residues generated in the process of smelting ores. At present, the metal gallium resources in China are relatively more, but the metal is extremely rare and is not easy to extract, and the separation technology is also limited. The most widely used method for extracting gallium at home and abroad at present is a solvent extraction method, and common extracting agents include carboxylic acids, phosphines, quinolines, amines and the like. The carboxylic acid extractant has good gallium separation effect and high extraction rate, but is very time-consuming and has a single research system. The phosphine extractant has better selective adsorptivity to gallium, but the whole extraction process needs to be carried out in a high-concentration hydrochloric acid solution, so that the damage to equipment and the increase of cost can be caused, and the environment can be polluted. Quinoline adsorbents are used in the alumina industry, but have not been widely used because of their long equilibration times and low extraction rates. The reaction system used by the amine extractant is a low-concentration acidic solution and is environment-friendly, but the gallium is difficult to separate from the iron.
The above methods for recovering gallium are not good in recycling, and are easy to cause environmental pollution, and the used reagents are expensive. In contrast, the adsorption method is considered to be the most effective method for extracting the scattered metals from the wastewater due to the advantages of low cost, low requirements for equipment, multifunction, simple operation and high reusability, and has become a hot spot for research at home and abroad. The adsorption method is a common method for recovering and removing target ions by mainly using a solid adsorbent to adsorb the target ions.
The carbon nano sheet material has the advantages of excellent stability, high specific surface area, abundant active sites and the like, and can be used as a carrier to be compounded with titanium dioxide, so that not only can various excellent characteristics of the carbon material be maintained, but also the stability and the reusability of the titanium dioxide can be enhanced, and the problem that the titanium dioxide is difficult to recycle can be effectively solved. The carbon nano-sheet and titanium dioxide composite material can be used as an adsorbent with higher adsorption selectivity, higher mechanical strength, excellent regeneration performance, better stability and low price.
Disclosure of Invention
The method comprises the steps of preparing tremella three-dimensional carbon nano-sheets by using sodium citrate as a carbon source through a direct carbonization method, and compounding hydroxyl-enriched titanium dioxide, sorbitol and the carbon nano-sheets. Titanium dioxide has many surface functional groups and can be used as an adsorbent to recover metal ions, but it is difficult to recycle and recycle the titanium dioxide in an aqueous solution because of its good water solubility. Therefore, the carbon material with high specific surface area and good chemical stability is used as a matrix to be combined with titanium dioxide rich in hydroxyl groups through C-O-Ti bonds, so that the hydrophilicity of the carbon material can be improved, the stability and the recycling property of the titanium dioxide can be improved, the related problem that the titanium dioxide is difficult to recycle is solved, the active adsorption sites of the material are increased, and the adsorption capacity of gallium is obviously improved.
The invention is realized by the following technical scheme: the tremella three-dimensional carbon nano sheet with modified hydroxyl groups is obtained by carbonizing tremella three-dimensional carbon nano sheet matrix at high temperature by sodium citrate, and the tremella three-dimensional carbon nano sheet matrix rich in hydroxyl groups is obtained by compounding butyl titanate and sorbitol on the tremella three-dimensional carbon nano sheet matrix.
The preparation method of the hydroxyl modified tremella three-dimensional carbon nano sheet comprises the following steps:
3) Firstly, placing sodium citrate into a porcelain boat for carbonization, washing with diluted hydrochloric acid and distilled water until the sodium citrate is neutral, and then placing the porcelain boat into a baking oven at 50 ℃ for drying overnight to obtain a carbon sample;
4) Taking the carbon sample obtained in the step 1), butyl titanate and sorbitol, ultrasonically stirring for 1.5 hours at room temperature, dropwise adding the obtained solution into distilled water, standing and settling for 24 hours, performing suction filtration, drying overnight, and grinding to obtain a target product.
In the preparation method of the hydroxyl modified tremella three-dimensional carbon nano sheet, in the step 1), carbonization is carried out for 2 hours in a nitrogen atmosphere at 800 ℃, and the heating rate is controlled to be 5 ℃ for min -1 。
In the preparation method, in the step 2), the carbon sample is sorbitol=1:0.1-0.7 according to the mass ratio, and the solid-liquid ratio of the carbon sample to butyl titanate is 1g: 10-20 mL.
The application of the hydroxyl modified tremella three-dimensional carbon nano sheet in gallium recovery.
The application method comprises the following steps: taking a solution containing 1000mg/L gallium ions, regulating the pH of the solution to 1, 2, 3 and 10, adding the hydroxyl modified tremella three-dimensional carbon nano-sheet in claim 1, vibrating and adsorbing for 24 hours at 30 ℃, filtering and drying.
The application comprises an elution step, wherein an eluent is added into the dried tremella three-dimensional carbon nano-sheet modified by hydroxyl groups and adsorbed with gallium ions, and the tremella three-dimensional carbon nano-sheet is taken out and filtered after shaking for 24 hours at 30 ℃.
In the application, the solid-to-liquid ratio of the hydroxyl modified tremella three-dimensional carbon nano sheet to the eluent is 10mg:10mL.
The eluent is at a concentration of 0.05mol.L -1 ～2mol·L -1 Or 0.05 mol.L -1 ～4mol·L -1 Is a HCl of (C).
In the application, the pH value of the gallium ion solution is 3 and 10; the concentration of the eluent is 2 mol.L -1 Is a HCl of (C).
The beneficial effects of the invention are as follows:
1) In the invention, tremella modified by hydroxylH in hydroxyl group on surface of three-dimensional carbon nano sheet + And Ga (OH) 2+ 、Ga(OH) 2 + 、Ga 3+ Cation exchange reaction occurs between the two to achieve the aim of absorbing gallium ions. The method is quick, simple and convenient, mild in reaction condition, large in gallium adsorption capacity and practical.
2) After six adsorption-analysis experiments, the recovery rate of gallium of the tremella three-dimensional carbon nano-sheet prepared by the invention can still reach more than 90%, which indicates that the tremella three-dimensional carbon nano-sheet modified by the hydroxy has better recycling capability and practical applicability.
3) In the mixed solution containing coexisting ions such as Ge (IV), zn (II), al (III) and Cu (II), the adsorption rate of the hydroxyl-modified tremella-shaped three-dimensional carbon nano-sheet to Ga (III) can still reach 87.4%, which indicates that other coexisting ions have less interference to the hydroxyl-modified tremella-shaped three-dimensional carbon nano-sheet.
4) The invention solves the problem that titanium dioxide is difficult to recycle in aqueous solution because the titanium dioxide is particularly easy to react with water, and breaks the limit of titanium dioxide used as a nontoxic harmless environment-friendly adsorption material in cyclic application.
5) The hydroxyl-modified tremella three-dimensional carbon nano-sheet prepared by the invention has the advantages that the adsorption rate of the hydroxyl-modified tremella three-dimensional carbon nano-sheet to Ga (III) can almost reach 100% when the pH is 3, and the maximum saturated adsorption quantity is 102.39mg g -1 。
In conclusion, the hydroxyl modified tremella three-dimensional carbon nano sheet prepared by the method can effectively adsorb rhenium ions, is quick and simple to prepare, has high adsorption rate, and has practical practicability.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a hydroxyl-modified tremella three-dimensional carbon nanosheet (3 DCN800-BT 10-S0.5).
Fig. 2 is a scanning electron microscope and a transmission electron microscope of a hydroxyl-modified tremella three-dimensional carbon nano sheet (3 DCN800-BT 10-S0.5), wherein A is a scanning electron microscope of 3DCN800, B is a transmission electron microscope of 3DCN800, C is a scanning electron microscope of 3DCN800-BT10-S0.5, and D is a transmission electron microscope of 3DCN800-BT10-S0.5.
Fig. 3 is a graph of the adsorption performance of hydroxyl-modified tremella three-dimensional carbon nanoplatelets (3 DCN800-BT 10-S0.5) on gallium at different acidity.
Fig. 4 is an adsorption isotherm of hydroxyl-modified tremella three-dimensional carbon nanoplatelets (3 DCN800-BT 10-S0.5) at ph=3 for gallium, where a is an adsorption isotherm of 3DCN800-BT10-S0.5 for Ga (III), B is an adsorption isotherm of 3DCN800-BT15-S0.5 for Ga (III), and C is an adsorption isotherm of 3DCN800-BT20-S0.5 for Ga (III).
FIG. 5 is a selective recovery of gallium in a mixed system of hydroxyl-modified tremella three-dimensional carbon nanoplatelets (3 DCN800-BT 10-S0.5).
Detailed Description
In order that the present invention may be more fully understood by those of ordinary skill in the art, the present invention will be described in more detail by the following non-limiting examples or comparative examples, which are not intended to limit the present invention in any way.
EXAMPLE 1 preparation of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets (3 DCN800-BT 10-S0.5)
(one) preparation
1) Putting 5g sodium citrate into porcelain boats, carbonizing at 800 deg.C under nitrogen atmosphere for 2 hr, and controlling the heating rate to 5 deg.C for min -1 The mixture was washed with diluted hydrochloric acid and distilled water until neutral, and then dried overnight in an oven at 50℃to give a carbon sample designated 3DCN800.
2) 1g of 3DCN800 obtained in the step 1), 10mL of butyl titanate and 0.5g of sorbitol are taken in a three-necked flask, after ultrasonic stirring is carried out for 1.5 hours at room temperature, the obtained solution is dropwise added into distilled water, standing and sedimentation are carried out for 24 hours, suction filtration operation is carried out, finally, drying is carried out overnight, and grinding is carried out to obtain the product which is named as 3DCN800-BT10-S0.5.
(II) detection
Scanning electron microscope, transmission electron microscope and functional group titration analysis: the scanning electron microscope and transmission electron microscope results of 3DCN800 and 3DCN800-BT10-S0.5 are shown as (A, B) and (C, D) in FIG. 2, and it can be seen from FIG. 2 that 3DCN800 and 3DCN800-BT10-S0.5 are a tremella-like three-dimensional carbon nano-sheet structure formed by interconnecting a plurality of curved carbon sheets. From Table 1 it can be seen that the surface functional group content of several different adsorbents. It can be seen that after butyl titanate and sorbitol are loaded on the three-dimensional carbon nano-sheet, the number of carboxyl functional groups is gradually reduced, the number of lactone groups is continuously increased, and it is presumed that the carboxyl groups on the surface of the carbon nano-sheet and the hydroxyl groups on the post-loaded butyl titanate have esterification reaction. The number of carboxyl groups and lactone groups is not changed before and after the sorbitol is loaded, and it is presumed that the hydroxyl groups on the sorbitol do not have esterification reaction with the carboxyl groups on the carbon nano-sheets, but are directly connected with the hydroxyl groups through hydrogen bonding.
TABLE 1 results of surface functional groups
Comparative example 1 three-dimensional carbon nanoplatelets (3 DCN 800)
Putting 5g sodium citrate into porcelain boats, carbonizing at 800 deg.C under nitrogen atmosphere for 2 hr, and controlling the heating rate to 5 deg.C for min -1 The mixture was washed with diluted hydrochloric acid and distilled water until neutral, and then dried overnight in an oven at 50℃to give a carbon sample designated 3DCN800.
EXAMPLE 2 preparation of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets (3 DCN800-BT 10-S0.1)
The procedure was as described in example 1, except that 0.1g of sorbitol was used instead of 0.5g of sorbitol in example 1, and the obtained hydroxyl-modified tremella-shaped three-dimensional carbon nanoplatelets were designated as 3DCN800-BT10-S0.1.
EXAMPLE 3 preparation of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets (3 DCN800-BT 10-S0.3)
The procedure was as described in example 1, except that 0.3g of sorbitol was used instead of 0.5g of sorbitol in example 1, and the obtained hydroxyl-modified tremella-shaped three-dimensional carbon nanoplatelets were designated as 3DCN800-BT10-S0.3.
EXAMPLE 4 preparation of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets (3 DCN800-BT 10-S0.7)
The procedure was as described in example 1, except that 0.7g of sorbitol was used instead of 0.5g of sorbitol in example 1, and the obtained hydroxyl-modified tremella-shaped three-dimensional carbon nanoplatelets were designated as 3DCN800-BT10-S0.7.
EXAMPLE 5 preparation of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets (3 DCN800-BT 15-S0.5)
The procedure of example 1 was followed, except that 15mL of butyl titanate was used instead of 10mL of butyl titanate in example 1, and the obtained hydroxyl-modified tremella-shaped three-dimensional carbon nanoplatelets were designated as 3DCN800-BT15-S0.5.
EXAMPLE 6 preparation of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets (3 DCN800-BT 20-S0.5)
The procedure of example 1 was followed, except that 20mL of butyl titanate was used instead of 10mL of butyl titanate in example 1, and the obtained hydroxyl-modified tremella-shaped three-dimensional carbon nanoplatelets were designated as 3DCN800-BT20-S0.5.
Example 7 adsorption Effect of hydroxyl-modified Tremella-like three-dimensional carbon nanosheets on gallium at different acidity
The method comprises the following steps: 10mg of the hydroxyl-modified tremella-shaped three-dimensional carbon nano-sheets prepared in examples 1-6 are respectively weighed and added into 10mL of the tremella-shaped three-dimensional carbon nano-sheet with the concentration of 20mg.L -1 In Ga (III) solution, the pH of the solution is adjusted to be 1, 2, 3 and 10 respectively, and the solution is subjected to oscillation adsorption for 24 hours at 30 ℃. The results are shown in FIG. 3.
As can be seen from fig. 3, the adsorption performance of the adsorbent to Ga (III) shows a tendency to increase and decrease at pH values of 1, 2, 3, 10. In addition, the adsorption rate of Ga (III) can almost reach 100% when the pH value of 3DCN800-BT10-S0.5 is 3 and 10, and the adsorption rate of Ga (III) when the pH value of the hydroxyl-modified tremella-shaped three-dimensional carbon nano-sheet prepared in examples 2-4 is 3 and 10 is lower than 90%. When the pH of the gallium solution is 4 to 9, gallium mainly exists in a white precipitate as a main form, and thus is not in the range of experimental consideration.
EXAMPLE 8 adsorption isotherms of hydroxyl-modified Tremella-like three-dimensional carbon nanoplatelets adsorbing Ga (III)
The method comprises the following steps: 10+/-0.2 mg of the hydroxyl-modified tremella-shaped three-dimensional carbon nano-sheets prepared in examples 1, 5 and 6 are respectively weighed, placed in Ga (III) solutions with the pH of 3 and the concentration of 50ppm by volume, and then vibrated for 24 hours at 30 ℃, and then the concentration of Ga (III) in the solutions and the concentration of stock solution at the time of balancing are measured. The results are shown in FIG. 4.
As can be seen from FIG. 4, the maximum saturated adsorption amounts of 3DCN800-BT10-S0.5, 3DCN800-BT15-S0.5 and 3DCN800-BT20-S0.5 for Ga (III) were 102.39mg, respectively -1 、63.89mg g -1 And 81.34mg g -1 . It can be summarized that 3DCN800-BT10-S0.5 has the best adsorption performance to Ga (III). From the linear correlation coefficient, the Langmuir adsorption isotherm model is the most consistent with experimental data, which shows that the adsorption of rhenium by 3DCN800-BT10-S0.5 belongs to monolayer adsorption.
Example 9 Selective recovery of gallium in Mixed System by hydroxyl-modified Tremella-like three-dimensional carbon nanoplatelets
The method comprises the following steps: weighing 10mg of the hydroxyl modified tremella three-dimensional carbon nano-sheet prepared in example 1, and adding the tremella three-dimensional carbon nano-sheet into 10mL of tremella three-dimensional carbon nano-sheet with the concentration of 20 mg.L -1 In Ge (IV), zn (II), al (III), cu (II) and Ga (III) solutions, the pH values of the solutions are respectively adjusted to be 1, 2, 3 and 10, and the solution is subjected to oscillation adsorption for 24 hours at 30 ℃. The results are shown in FIG. 5.
At pH 3, the adsorbent has a certain adsorption effect on Ge (IV), al (III) and Cu (II), while at other acidity conditions, 3DCN800-BT10-S0.5 is basically not adsorbed on Ge (IV), zn (II), al (III) and Cu (II). When the pH of the mixed solution is 3, the adsorption rate of the adsorbent to Ga (III) can still reach 87.4%, which shows that the interference of coexisting ions to Ga (III) adsorption of 3DCN800-BT10-S0.5 is small.
Example 10 elution Effect of different eluents on gallium-adsorbed hydroxyl-modified Tremella-like three-dimensional carbon nanosheets
The method comprises the following steps: 150mg of 3DCN800-BT10-S0.5 prepared in example 1 was weighed and added to 150mL of Ga (III) solution with a concentration of 50ppm, respectively, and after shaking adsorption for 24 hours at 30 ℃, the samples were filtered and taken out to determine the concentration of gallium ions in the stock solution and the filtrate, respectively. Then, 10mg of the gallium-loaded adsorbent 3DCN800-BT10-S0.5 was weighed, 10mL of hydrochloric acid and sodium hydroxide with different concentrations were added for elution, and the gallium ion concentration was measured after shaking at constant temperature for 24 hours under the condition of 303K, and the results are shown in Table 2.
TABLE 2 elution effects of different eluents on gallium ions
As is clear from Table 2, the concentration was 2 mol.L -1 The elution effect of HCl on gallium-adsorbed 3DCN800-BT10-S0.5 is best and can reach 92.60 percent.
Claims (1)
1. The application of the hydroxyl modified tremella three-dimensional carbon nano sheet in gallium recovery is characterized by comprising the following steps:
weighing 10mg of hydroxyl modified tremella three-dimensional carbon nano-sheet, and adding into 10mL of tremella three-dimensional carbon nano-sheet with concentration of 20mg.L -1 Adjusting the pH of the solution to 3 in Ga (III) solution, and oscillating and adsorbing for 24 hours at 30 ℃;
the preparation method of the hydroxyl modified tremella three-dimensional carbon nano-sheet comprises the following steps:
1) Placing 5g sodium citrate into porcelain boats, carbonizing at 800 deg.C under nitrogen atmosphere for 2 hr, and controlling heating rate to 5 deg.C for min -1 Washing with diluted hydrochloric acid and distilled water until neutral, and then drying overnight in an oven at 50deg.C to obtain a carbon sample designated as 3DCN800;
2) Taking 3DCN800, 10mL butyl titanate and 0.5g sorbitol obtained in the step 1) of 1g, putting the obtained solution into a three-neck flask, stirring the solution in an ultrasonic manner at room temperature for 1.5 hours, dropwise adding the solution into distilled water, standing and settling the solution for 24 hours, performing suction filtration operation, drying the solution overnight, and grinding the solution to obtain the hydroxyl modified tremella-shaped three-dimensional carbon nano sheet.
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