CN113926429A - Hydroxyl modified titanium dioxide composite material, preparation method thereof and application thereof in germanium recovery - Google Patents
Hydroxyl modified titanium dioxide composite material, preparation method thereof and application thereof in germanium recovery Download PDFInfo
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- CN113926429A CN113926429A CN202111358834.6A CN202111358834A CN113926429A CN 113926429 A CN113926429 A CN 113926429A CN 202111358834 A CN202111358834 A CN 202111358834A CN 113926429 A CN113926429 A CN 113926429A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a hydroxyl modified titanium dioxide composite material, a preparation method thereof and application thereof in germanium recovery. The technical scheme is as follows: taking a certain amount of butyl titanate and n-propanol, uniformly mixing, respectively adding the mixture into tartaric acid, malic acid or succinic acid solution with a certain concentration, stirring at 65 ℃ for 2h, stirring the obtained suspension for 12h, washing to neutrality, and drying. And adding the intermediate product into a sodium hydroxide solution, stirring for 0.5h, and washing to be neutral to obtain the titanium dioxide composite material modified by different amounts of hydroxyl groups. The surface of the titanium dioxide composite material modified by hydroxyl contains a large number of hydroxyl functional groups, germanium can be selectively adsorbed from a mixed solution of Cu, Al, Zn, Si and Ge, and the titanium dioxide composite material modified by hydroxyl has the advantages of low cost, simple preparation, good stability and no toxicity.
Description
Technical Field
The invention belongs to the technical field of preparation of composite materials and extraction of scattered metals, and particularly relates to a preparation method of a hydroxyl modified titanium dioxide composite material and application of the hydroxyl modified titanium dioxide composite material in germanium recovery.
Background
Germanium is a rare element, is rich in germanium resources in China, has the first storage capacity in the world, and is widely applied to the fields of semiconductors, aerospace measurement and control, nuclear physical detection, optical fiber communication, infrared optics, solar cells, chemical catalysts, biomedicine and the like. It has been found that 11 kinds of germanium minerals exist mainly in nanometer germanium-silicon, germanite, calcium germanium alum, germanium-lead alum, germanium-iron ore and germanium magnetite, but germanium has no independent deposit in the earth crust, is mostly associated with non-ferrous metal minerals, has low content and wide distribution, and at present, mainly extracts germanium from zinc smelting and coal-fired byproducts.
At present, there are many methods for recovering germanium, including chlorination distillation, resin adsorption, microemulsion, zinc powder displacement, ion exchange, extraction, and electrolysis, as well as acid leaching, alkaline leaching, combination, and vacuum melting. The solvent extraction method is an important method for separating and enriching germanium. The commonly used germanium extractants can be broadly divided into three categories: the first is hydroxames represented by LIX 63 and quinolines represented by Kelex100, and most of the extractants are foreign products; secondly, amine extractant, namely N235 exists in China, but no industrial application example exists; thirdly, hydroximic acids, such as H106 (tridecyl tertiary carbon hydroxamic acid), YW100, 7815, HGS98 and the like, are generally developed domestically, but the extracting agents still have one or more problems in industrial application. The functional groups of the extracting agent for adsorbing germanium are hydroxyl, carboxyl and the like, so the extracting agent takes titanium dioxide as a matrix, and hydroxyl modification is carried out on the titanium dioxide by utilizing the excellent surface performance of the titanium dioxide, so that the adsorption capacity for germanium is improved.
Meanwhile, titanium dioxide is a nontoxic inorganic substance and contains a large number of oxygen-containing functional groups on the surface. Compared with metal oxides of other semi-metal semiconductor materials, the titanium dioxide has high polarity of Ti-O bonds, and water adsorbed on the surface is dissociated due to polarization to easily form hydroxyl. The surface hydroxyl can improve the performance of titanium dioxide as an adsorbent and various monomers, and provides convenience for surface modification. However TA-TiO2And MA-TiO2The crystallinity of the crystal is destroyed by exposing a large amount of hydroxyl groups after the treatment with sodium hydroxide. The surface of the titanium dioxide modified by tartaric acid, malic acid and succinic acid contains a large amount of Ti-O-H, and the Ti-O-H has higher adsorption capacity to germanium ions.
Disclosure of Invention
The invention mainly utilizes the superior surface property of titanium dioxide, adds organic acid solution into the titanium dioxide to obtain the functionalized titanium dioxide adsorbent, and the crystallinity of the crystal is damaged due to the exposure of a large amount of hydroxyl after the treatment of sodium hydroxide. The isoelectric points of the three titanium dioxide adsorbents modified by the organic acid solution are reduced, so that the adsorption performance to germanium is improved. The method has the advantages of simple operation, environmental protection, cleanness, high resource utilization rate, high selectivity to germanium, short treatment period, cyclic utilization and high practical value.
The invention is realized by the following technical scheme that the preparation method of the titanium dioxide composite material modified by hydroxyl comprises the following steps:
1) mixing butyl titanate and n-propanol solution, respectively adding the mixed solution into organic acid solution, carrying out reaction, carrying out suction filtration, washing to be neutral, and drying to obtain an intermediate product;
2) dissolving sodium hydroxide in deionized water, and adjusting the concentration to be 1 mol.L-1Adding the intermediate product, uniformly mixing, stirring the mixture at room temperature for 0.5h, performing suction filtration, and washing to be neutral to obtain a target product, namely the titanium dioxide composite material modified by different hydroxyl numbers.
In the above hydroxyl-modified titanium dioxide composite material, in step 1), the organic acid solution is one or more of tartaric acid, malic acid, gluconic acid and succinic acid.
In the step 1), the reaction is carried out at 65 ℃ for 12 hours.
In the above hydroxyl-modified titanium dioxide composite material, in step 1), the ratio by volume of butyl titanate: n-propanol-5: 2.
The hydroxyl modified titanium dioxide composite material comprises the following components in percentage by volume: the concentration of the organic acid solution is 1:4, and the concentration of the organic acid solution is 0.16 mol.L-1。
The application of the titanium dioxide composite material modified by hydroxyl in germanium recovery.
In the application, the pH value of the germanium ion-containing solution is adjusted to be 8-10, the hydroxyl modified titanium dioxide composite material is added, and the oscillation adsorption is carried out for 24-48 h.
The application comprises eluting with 0.5-1.5 mol.L of eluent-1Of HCl (g).
TA-TiO of the invention2The synthetic route for-OH is as follows:
the invention has the beneficial effects that:
1. the raw material has excellent performance: the invention takes titanium dioxide as a raw material, has excellent surface property, and prepares the functionalized titanium dioxide adsorbing material with high-efficiency selectivity on germanium, and the material can stably exist at the temperature lower than 150 ℃.
2. The operation is simple and convenient: the invention compounds the titanium dioxide and the modified solution by a simple chemical treatment method, and the synthesis process is simple and safe.
3. The cost is low: the titanium dioxide and the modified solution used in the invention have low price, the processing method is relatively simple, and the cost is greatly reduced.
4. In the invention, the composite material has larger adsorption capacity to germanium in the waste liquid under certain acidity, and 0.5-1.5 mol.L is adopted-1Of HCl (g). The adsorbed germanium can be eluted efficiently.
5. The titanium dioxide composite material modified by hydroxyl groups prepared by the invention can selectively adsorb germanium from high-concentration Cu, Al, Zn, Si and Ge mixed solution, and can realize the recovery of germanium from actual feed liquid.
6. The titanium dioxide surface of the invention contains a large amount of hydroxyl groups, and Ti-O-H is formed after the organic acid solution is added, and the Ti-O-H has higher adsorption capacity to germanium ions.
7. The hydroxyl modified titanium dioxide composite material prepared by the invention can recover germanium from germanium waste liquid, and the titanium dioxide used for preparing the composite material is low in price, rich in source and strong in practical application capability.
Drawings
FIG. 1 is a scanning electron micrograph of the hydroxyl-modified titanium dioxide composite prepared in example 1.
Fig. 2 is an infrared image of the titanium dioxide and tartaric, malic or succinic acid composite material and the hydroxyl-modified titanium dioxide composite material prepared in example 1.
Fig. 3 is a graph of the adsorption efficiency of the titanium dioxide and tartaric acid, malic acid or succinic acid composite material prepared in example 2 and the titanium dioxide composite material modified by hydroxyl groups on Ge at different pH.
Fig. 4 is a statistical graph of the separation effect of the hydroxyl group-modified titanium dioxide composite material and the titanium dioxide and tartaric acid, malic acid or succinic acid composite material prepared in example 1 on germanium from the mixed solution (Cu, Al, Zn, Si, Ge).
Detailed Description
Example 1 hydroxyl-modified titanium dioxide composite
(I) preparation method
1) 50mL of a mixture of butyl titanate and 20mL of n-propanol were added to 200mL of 0.16 mol. L-1Then stirring the mixture for 2 hours at 65 ℃, then stirring the suspension for 12 hours at room temperature, finally washing the white solid to be neutral by deionized water, then drying the white solid for 24 hours at 50 ℃, and respectively naming the obtained intermediate products as TA-TiO2、MA-TiO2And SU-TiO2。
2) 0.5g of the above intermediate product was added to 1.0 mol. L-1Stirring the solution for 0.5h, washing the product to be neutral by deionized water, and respectively naming the finally obtained product as TA-TiO2-OH、MA-TiO2-OH and SU-TiO2-OH。
(II) results
1) FIG. 1 shows TA-TiO, respectively2-OH、MA-TiO2-OH and SU-TiO2Scanning electron micrograph of-OH, wherein TA-TiO2-OH and MA-TiO2the-OH surfaces are substantially similar in morphology and all present microspheres of relatively uniform shape and size. SU-TiO2The surface morphology of-OH is much different from that of the former, and the surface is rough and porous and has no regular shape.
2) FIG. 2 shows TA-TiO, respectively2、TA-TiO2-OH、MA-TiO2、MA-TiO2-OH、SU-TiO2、SU-TiO2-infrared spectrum of OH. At 3500cm-1And 1650cm-1The absorption peak is the stretching vibration peak of-OH and C ═ O, 1385cm-11200cm in-plane bending vibration peak at Ti-OH-1Is located at the stretching vibration peak of C-O, 650cm-1The out-of-plane bending vibration peak is O-H. Comparative TA-TiO2And TA-TiO2-OH、MA-TiO2And MA-TiO2-OH、SU-TiO2And SU-TiO2The infrared spectrogram of-OH can find that the TA-TiO treated by the sodium hydroxide2-OH、MA-TiO2-OH and SU-TiO2The stretching vibration peak of-OH, the stretching vibration peak of C ═ O, and the in-plane bending vibration peak of Ti-OH all become stronger accordingly. This is probably because the addition of sodium hydroxide destroys the dimer structure which is easily formed, so that the hydroxyl groups are exposed, and a certain amount of hydroxyl groups are added on the surface of titanium dioxide, so that the peak intensity is correspondingly enhanced.
Example 2 adsorption Effect of hydroxyl-modified titanium dioxide composite on germanium at different acidity
10mg each of the TA-TiO compounds prepared in example 1 were taken2、MA-TiO2、SU-TiO2、TA-TiO2-OH、MA-TiO2-OH and SU-TiO2-OH. Adding into 10mL of 20ppm germanium solution with pH of 2, 4, 6, 8, 10, respectively, placing into a shaking box, shaking at 303k for 24h at rotation speed of 180r/min, filtering, and measuring the adsorption rate of the filtrate and stock solution. The results are shown in FIG. 3.
As can be seen from FIG. 3, as the pH value increased, SU-TiO2The adsorption rate of germanium is relatively high and can reach 86.17 percent at most. And TA-TiO at pH 102And MA-TiO2The adsorption efficiency of germanium only reaches 34.63 percent and 51.50 percent.
Example 3 adsorption Effect of hydroxyl-modified titanium dioxide/tartaric acid composite on germanium in Mixed solution
100 mg.L under different acidity is prepared-1The mixed solution of Cu, Al, Zn, Si and Ge is shaken in a shaking box for 24 hours under the condition that the solid-to-liquid ratio is 1:1, filtered, and the concentration of each metal ion before and after adsorption is measured by using ICP-OES, and the obtained result is shown in figure 4.
As can be seen from FIG. 4, TA-TiO is present over the entire range of acidity2The adsorption efficiency of-OH on germanium is always higher than that of other metal ions, which shows that TA-TiO2the-OH has better adsorption selectivity to germanium. The composite material synthesized by the invention can selectively recover germanium from waste water containing mixed ions.
EXAMPLE 4 elution Effect of acid-base solutions of varying concentrations on germanium-loaded composites
1) Weighing 100mg of cases1 preparation of TA-TiO2300 mg.L of-OH at pH 3-1Taking out the germanium solution after shaking for 48h, filtering, measuring the concentration of germanium ions in the stock solution and the filtrate, and calculating to obtain 100mgTA-TiO2The amount of-OH-supported germanium was 77.0mg g-1。
2) Weighing 10mg of TA-TiO loaded with germanium2OH, adding 10mL of sodium hydroxide, hydrochloric acid or water with different concentrations as eluent to the TA-TiO loaded with germanium2-OH for elution. The results are shown in Table 1
3) As shown in Table 1, the HCl concentration was 0.5 to 1.5 mol.L-1The elution effect on germanium is better, 0.5 mol.L-1The elution rate of the HCl eluent (1.5 mol. L) on germanium was 72.75%-1The elution rate of the HCl eluent (1 mol. L) on germanium was 83.57%-1The HCl has the best effect of eluting germanium, and can reach 93.88 percent.
TABLE 1 elution Effect of different eluents on germanium
Example 5 Recycling of hydroxyl modified titanium dioxide and tartaric acid composites for germanium recovery
The method comprises the following steps: 100mg of TA-TiO was taken2OH in 100mL, 20 mg. L-1In the germanium solution (2), 1 mol. L is used after adsorption equilibrium and filtration-1The HCl was eluted and the results are shown in table 2. As can be seen from the data in the table, after five times of adsorption-elution experiments, TA-TiO2The recovery rate of the-OH to the germanium can still reach more than 80 percent, and the recovery rate can be seen as TA-TiO2the-OH has better regeneration capability.
TABLE 2 TA-TiO2Adsorption elution cycle table for-OH
Claims (8)
1. A hydroxyl modified titanium dioxide composite material is characterized in that: the preparation method comprises the following steps:
1) mixing butyl titanate and n-propanol solution, respectively adding the mixed solution into organic acid solution, carrying out reaction, carrying out suction filtration, washing to be neutral, and drying to obtain an intermediate product;
2) dissolving sodium hydroxide in deionized water, and adjusting the concentration to be 1 mol.L-1Adding the intermediate product, uniformly mixing, stirring the mixture at room temperature for 0.5h, performing suction filtration, and washing to be neutral to obtain a target product, namely the titanium dioxide composite material modified by different hydroxyl numbers.
2. The hydroxyl-modified titanium dioxide composite material of claim 1, wherein: in the step 1), the organic acid solution is one or more than two of tartaric acid, malic acid, gluconic acid and succinic acid.
3. The hydroxyl-modified titanium dioxide composite material of claim 2, wherein: in the step 1), the reaction is carried out for 12 hours at 65 ℃.
4. A hydroxyl-modified titanium dioxide composite material according to claim 3, wherein: in the step 1), according to the volume ratio, butyl titanate: n-propanol-5: 2.
5. The hydroxyl-modified titanium dioxide composite material of claim 4, wherein: according to volume ratio, butyl titanate: the concentration of the organic acid solution is 1:4, and the concentration of the organic acid solution is 0.16 mol.L-1。
6. Use of a hydroxyl modified titanium dioxide composite material according to any one of claims 1 to 5 for the recovery of germanium.
7. The use according to claim 6, characterized in that the method is as follows: adjusting the pH value of the germanium ion-containing solution to be 8-10, adding the hydroxyl-modified titanium dioxide composite material according to any one of claims 1-5, and oscillating and adsorbing for 24-48 h.
8. Use according to claim 7, characterized in that the method is as follows: eluting with an eluent, wherein the eluent is 0.5-1.5 mol.L-1Of HCl (g).
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| CN115785707A (en) * | 2022-11-30 | 2023-03-14 | 江苏集萃道路工程技术与装备研究所有限公司 | Environment-friendly anticorrosive paint for highway steel guardrail and preparation method and application thereof |
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| CN106732432A (en) * | 2017-01-17 | 2017-05-31 | 辽宁大学 | A kind of shitosan/persimmon tannin composite and preparation method thereof and the application in Ti recovery |
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Application publication date: 20220114 |