Aerogel GCP composite electrode material, preparation method thereof and application of aerogel GCP composite electrode material in electro-adsorption recovery of rhenium
By preparing aerogel GCP composite electrode material and utilizing the combination of ginger carboxymethyl cellulose and polyaniline, the problem of rhenium resource shortage was solved, and efficient, low-cost and environmentally friendly rhenium recycling was achieved.
Patent Information
- Application Number
- CN202511565740.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-30
- Publication Date
- 2025-12-19
AI Technical Summary
Rhenium resources are scarce and cannot be obtained through traditional mineral mining. Existing recycling technologies are inefficient, costly, and cause significant environmental pollution.
The aerogel GCP composite electrode material is prepared by combining ginger carboxymethyl cellulose and polyaniline. It forms a conductive aerogel through hydrogen bonding and is used for electro-adsorption and recovery of rhenium in wastewater. The operation is simple and environmentally friendly.
It achieves efficient rhenium recovery, with excellent adsorption performance, simple operation, low environmental pollution, low cost, and an adsorption capacity of up to 297.08 mg·g-1.
Smart Images
Figure CN121158905A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of rhenium electroadsorption technology, specifically relating to an aerogel GCP composite electrode material, its preparation method, and its application in rhenium electroadsorption recovery. Background Technology
[0002] Rhenium (Re) is one of the world's most important and scarce resources. Due to its high melting point and excellent ductility, it is widely used in aerospace, petrochemicals, unleaded gasoline catalytic reactions, electronics, and other fields. It is a key metal of significant value in military strategy and high-end manufacturing. Large-scale mining of rhenium faces two major challenges: 1) Extremely low reserves. The abundance of rhenium in the Earth's crust is only about 0.4 × 10⁻⁶. -9 1) Overall reserves are scarce; 2) No independent minerals exist. There are no independent minerals in nature with rhenium as the main component, making it impossible to directly obtain large quantities of rhenium ore through traditional mining. Because direct extraction is difficult, industrially used rhenium mainly comes from wastewater generated during copper-molybdenum smelting, where rhenium is primarily in the form of ReO4. - Rhenium exists in various forms. Currently, global reserves are approximately 2,300 tons, mainly distributed in countries such as Chile, Russia, the United States, and Kazakhstan. China has scarce rhenium resources, with reserves of approximately 200 tons, and these resources are becoming increasingly scarce with technological advancements.
[0003] Currently, rhenium recovery technologies mainly include precipitation, extraction, ion exchange, and adsorption. Among these, electroadsorption technology has attracted widespread attention due to its high efficiency in removing heavy metal ions and is considered to have potential application value in the recovery of rare and dispersed metal ions. By introducing low-cost natural polymers and conductive polymers with high pseudocapacitance into electrode materials, not only can the specific capacitance and structural stability of the materials be significantly improved, but excellent conductivity can also be maintained. This provides new ideas and research directions for achieving efficient and sustainable recovery of rhenium resources. Summary of the Invention
[0004] This invention addresses the increasingly scarce rhenium resources by providing an aerogel GCP composite electrode material, its preparation method, and its application in the electroadsorption recovery of rhenium. This invention fully utilizes the natural structure of biomass cellulose and the conductivity of polyaniline to prepare a conductive aerogel with superior electrochemical properties through supramolecular composite synthesis via hydrogen bonding without the use of any chemical crosslinking agents. The invention also applies this conductive aerogel to the electrochemical extraction of rhenium from wastewater.
[0005] The technical solution adopted in this invention is: an aerogel GCP composite electrode material, which is an aerogel GCP composite electrode material formed by combining ginger carboxymethyl cellulose (GCNF) and polyaniline (PANI).
[0006] A method for preparing an aerogel GCP composite electrode material includes the following steps:
[0007] 1) Preparation of ginger carboxymethyl cellulose (GCNF): Citric acid, choline chloride and water were mixed evenly to obtain a uniform and transparent eutectic solvent. Then ginger powder was added, heated and stirred, washed and dried to obtain ginger carboxymethyl cellulose (GCNF).
[0008] 2) Preparation of polyaniline: Ammonium persulfate was dissolved in hydrochloric acid, and the resulting solution was slowly added dropwise to the hydrochloric acid solution of aniline. The mixture was continuously stirred in an ice-water bath, washed, and dried to obtain polyaniline (PANI).
[0009] 3) Dissolve ginger carboxymethyl cellulose (GCNF) in deionized water, dissolve polyaniline (PANI) in hydrochloric acid, mix the GCNF aqueous solution and PANI hydrochloric acid solution, stir evenly, and freeze dry to obtain aerogel GCP composite electrode material.
[0010] Further, in step 1), the mass ratio of citric acid:choline chloride:water is (5-7):(1.5-2.5):(1.5-2.5).
[0011] Further, in step 1), the heating and stirring are performed at a heating temperature of 120℃-140℃ and a stirring time of 3h-4h.
[0012] Further, in step 2), the mass ratio of ammonium persulfate to aniline is (1.0-1.5):1.
[0013] Further, in step 3), the mass ratio of ginger carboxymethyl cellulose (GCNF): polyaniline (PANI) is 1:(1-3).
[0014] This invention provides the application of an aerogel GCP composite electrode material in the electroadsorption recovery of rhenium.
[0015] Further, the method is as follows: A two-electrode electroadsorption device is used. After the aerogel GCP composite electrode material is mixed evenly with PVDF and conductive carbon black, a small amount of N-methylpyrrolidone is added dropwise. After mixing evenly, the mixture is coated onto a carbon plate and dried. The resulting electrode is used as the anode; the carbon rod is used as the cathode; and the rhenium-containing wastewater is used as the electrolyte. An external voltage is applied through a constant voltage power supply to electroadsorb Re(VII) in the solution.
[0016] Furthermore, by mass ratio, the aerogel GCP composite electrode material:PVDF:conductive carbon black = (7-9):(0.5-1.5):(0.5-1.5); the drying temperature is 70℃-90℃, and the drying time is 12h-14h.
[0017] Furthermore, the pH of the rhenium-containing wastewater was adjusted to 1-5; an external voltage of 0.5V-1.4V was applied; and the electro-adsorption time was 1-2 hours.
[0018] The beneficial effects of this invention are:
[0019] 1. The aerogel GCP composite electrode material provided by the present invention serves as the anode. Re(VII) ions migrate to the vicinity of the anode working electrode under the action of electric field force, and are then electrostatically attracted and adsorbed onto the surface of the electrode material by the hydrochloric acid functional groups doped on the electrode surface. Through ion exchange, rhenium in wastewater can be effectively adsorbed.
[0020] 2. The method for synthesizing aerogel GCP composite electrode material provided by the present invention is simple to operate, does not require high temperature and high pressure, the raw materials are cheap and the environmental pollution is small. Using aerogel GCP composite electrode material as an adsorbent material, it can effectively adsorb rhenium in wastewater.
[0021] 3. The aerogel GCP composite electrode material provided by this invention exhibits excellent adsorption performance, with the optimal adsorption effect for rhenium at pH=4, and a saturated adsorption capacity of up to 297.08 mg·g⁻¹. -1 . Attached Figure Description
[0022] Figure 1 This is a flowchart illustrating the synthesis process of the aerogel GCP composite electrode material of the present invention.
[0023] Figure 2 This is a CV curve of the aerogel GCP composite electrode material of the present invention at different scan rates.
[0024] Figure 3 This invention relates to the constant current charge-discharge test of the aerogel GCP composite electrode material under different current densities.
[0025] Figure 4 This is a schematic diagram of the electroadsorption of Re(Ⅶ) by the aerogel GCP composite electrode material of the present invention.
[0026] Figure 5 This study investigates the effect of different pH values on the adsorption performance of rhenium by the aerogel GCP composite electrode material of this invention.
[0027] Figure 6 This describes the effect of different voltages on the adsorption performance of rhenium by the aerogel GCP composite electrode material of this invention.
[0028] Figure 7 This is a graph showing the change in the adsorption capacity of rhenium by the aerogel GCP composite electrode material of this invention over time.
[0029] Figure 8 This is the adsorption isotherm of rhenium adsorbed by the aerogel GCP composite electrode material of this invention.
[0030] Figure 9 These are the infrared spectra of the raw materials and the aerogel GCP composite electrode material of this invention before and after adsorption. Detailed Implementation
[0031] Example 1 Aerogel GCP Composite Electrode Material
[0032] (a) Preparation method:
[0033] Synthetic routes such as Figure 1 The method includes the following steps:
[0034] 1. Preparation of ginger carboxymethyl cellulose (GCNF):
[0035] According to the mass ratio of citric acid:choline chloride:water = 6:2:2, 60g of citric acid, 20g of choline chloride and 20g of water were stirred evenly at 80℃ to obtain a uniform and transparent eutectic solvent. Then, 4.5g of ginger powder was added, and the mixture was mechanically stirred at 130℃ and 800r for 3h. After washing, it was dried in an oven at 80℃ to obtain ginger carboxymethyl cellulose (GCNF).
[0036] 2) Preparation of polyaniline:
[0037] Based on a molar ratio of ammonium persulfate to aniline of 1.25:1, 3.13 g of ammonium persulfate was dissolved in 125 mL of 1 M hydrochloric acid. 1 mL of aniline was dissolved in 125 mL of 1 M hydrochloric acid. The ammonium persulfate solution was slowly added dropwise to the aniline solution, and the mixture was stirred continuously in an ice-water bath for 12 hours. After washing, the mixture was dried under vacuum at 60 °C to obtain polyaniline (PANI).
[0038] 3) Preparation of aerogel GCP composite electrode material:
[0039] According to the mass ratio of GCNF:PANI = 1:2, 0.1g of ginger carboxymethyl cellulose (GCNF) was dissolved in 5mL of deionized water, and 0.2g of polyaniline (PANI) was dissolved in 5mL of 0.1M hydrochloric acid. The GCNF aqueous solution and the PANI hydrochloric acid solution were mixed, stirred evenly, and then freeze-dried for 12h to obtain the aerogel GCP composite electrode material, labeled as GCP-2.
[0040] (ii) Characterization
[0041] Figure 2 This is a cyclic voltammetry (CV) curve of the aerogel GCP composite electrode material of this invention at different scan rates from 1mV to 10mV. Figure 2 As shown, the CV curves of the aerogel GCP composite electrode material at different scan rates all show a linear increase in volt-ampere current with increasing scan rate, proving that the aerogel GCP composite electrode material possesses pseudocapacitive characteristics. Figure 2As shown, the aerogel GCP composite electrode material has two pairs of redox peaks because polyaniline is divided into a fully reduced state and a fully oxidized state.
[0042] Figure 3 This invention relates to the constant current charge-discharge test of the aerogel GCP composite electrode material under different current densities. For example... Figure 3 As shown, constant current charge-discharge tests were performed on the aerogel GCP composite electrode material. At different current densities ranging from 1 A / g to 5 A / g, the constant current charge-discharge curves of the aerogel GCP composite electrode material did not exhibit the standard triangle of double-layer capacitance, conforming to the constant current charge-discharge curve of pseudocapacitive charge storage. A larger specific capacitance was observed at a current density of 5 A / g.
[0043] Example 2: Application of aerogel GCP composite electrode material in the electroadsorption recovery of rhenium
[0044] The electro-adsorption device using two electrodes is described below:
[0045] 1. According to the mass ratio of aerogel GCP composite electrode material:PVDF:conductive carbon black = 8:1:1, after the aerogel GCP composite electrode material is mixed evenly with PVDF and conductive carbon black, a small amount of N-methylpyrrolidone is added dropwise, mixed evenly, and then coated onto a carbon plate and dried at 80℃ for 12h. The resulting electrode is used as the anode.
[0046] 2. A carbon rod is used as the cathode.
[0047] 3. Using rhenium-containing wastewater as the electrolyte, adjust the pH of the rhenium-containing wastewater to 1-5; apply an external voltage of 0.5V-1.4V through a constant voltage power supply, and perform electroadsorption for 1-2 hours to adsorb Re(VII) in the solution.
[0048] Figure 4 This is a schematic diagram of the electroadsorption of Re(VII) by the aerogel GCP composite electrode material of this invention. Figure 4 As shown, the aerogel GCP composite electrode material is used as the anode and the carbon rod is used as the cathode. An external voltage is applied through a constant voltage power supply, and an electric field force is applied at the electrode / electrolyte solution interface to make the negatively charged Re(Ⅶ) in the solution move towards the electrode with the opposite charge.
[0049] (I) Effect of different pH values on the adsorption performance of rhenium by aerogel GCP composite electrode material
[0050] Method: Take 50 mL of rhenium with a concentration of 100 mg·L⁻¹ -1 Rhenium-containing wastewater was used as the electrolyte, and the pH of the rhenium-containing wastewater was adjusted to 1, 2, 3, 4, and 5 respectively. An external voltage of 1.2V was applied through a constant voltage power supply, and electro-adsorption was performed for 2 hours to adsorb Re(VII) in the solution.
[0051] Figure 5This describes the effect of different pH values on the rhenium adsorption performance of the aerogel GCP composite electrode material of this invention. For example... Figure 5 As shown, the adsorption effect varies at different pH values, and acidity is a key factor affecting the electrochemical extraction performance of rhenium. When the pH is greater than 4, polyaniline undergoes some deprotonation, leading to a decrease in adsorption capacity. When the pH is less than 4, the number of interfering anions in the solution increases, resulting in a further decrease in adsorption capacity. The adsorption capacity reaches its maximum at pH 4, reaching 139.06 mg·g⁻¹. -1 Therefore, in this invention, the pH of the rhenium-containing wastewater is preferably adjusted to 4.
[0052] (II) Effect of different voltages on the adsorption performance of rhenium by aerogel GCP composite electrode material
[0053] Method: Take 50 mL of rhenium with a concentration of 100 mg·L⁻¹ -1 Rhenium-containing wastewater was used as the electrolyte, and the pH of the rhenium-containing wastewater was adjusted to 4. External voltages of 0.6V, 0.8V, 1.0V, 1.2V, and 1.4V were applied through a constant voltage power supply, and electro-adsorption was performed for 2 hours to adsorb Re(VII) in the solution.
[0054] Figure 6 This describes the effect of different voltages on the rhenium adsorption performance of the aerogel GCP composite electrode material of this invention. For example... Figure 6 As shown, voltage is also a key factor affecting the electrochemical extraction performance of rhenium. The adsorption effect varies at different voltages. Below 1.2V, the adsorption capacity increases with increasing voltage; above 1.2V, water in the solution begins to be electrolyzed, leading to a decrease in adsorption capacity. At the optimal adsorption voltage of 1.2V, the adsorption capacity can reach 139.13 mg·g⁻¹. -1 Therefore, in this invention, it is preferable to apply an external voltage of 1.2V through a constant voltage power supply.
[0055] (III) Adsorption kinetics of rhenium adsorbed by different proportions of GCP-n
[0056] 1. Preparation of aerogel GCP composite electrode material (GCP-1):
[0057] The method is the same as in Example 1, except that, by mass ratio, GCNF:PANI = 1:1, 0.1g of ginger carboxymethyl cellulose (GCNF) is dissolved in 5mL of deionized water, and 0.1g of polyaniline (PANI) is dissolved in 5mL of 0.1M hydrochloric acid.
[0058] 2. Preparation of aerogel GCP composite electrode material (GCP-3):
[0059] The method is the same as in Example 1, except that, by mass ratio, GCNF:PANI = 1:3, 0.1g of ginger carboxymethyl cellulose (GCNF) is dissolved in 5mL of deionized water, and 0.3g of polyaniline (PANI) is dissolved in 5mL of 0.1M hydrochloric acid.
[0060] 3. Adsorption methods:
[0061] Method: Take 50 mL of rhenium with a concentration of 100 mg·L⁻¹ -1 Rhenium-containing wastewater was used as the electrolyte, and the pH of the rhenium-containing wastewater was adjusted to 4. An external voltage of 1.2V was applied through a constant voltage power supply, and the concentration of rhenium in the solution after adsorption was tested at intervals of 1 min, 3 min, 5 min, 10 min, 20 min, 30 min, 60 min, 90 min, and 120 min.
[0062] Figure 7 This is a graph showing the change in the adsorption capacity of rhenium by three aerogel GCP composite electrode materials over time. Figure 7 As shown, the adsorption of the three aerogel GCP composite electrode materials basically reached equilibrium after 120 min, and the composite electrode material prepared with a GCNF to PANI mass ratio of 1:2 had the best adsorption effect.
[0063] (iv) Adsorption isotherm of rhenium by aerogel GCP composite electrode material
[0064] Figure 8 The adsorption isotherm of the aerogel GCP composite electrode material GCP-2 prepared in Example 1 adsorbs rhenium. Three typical adsorption isotherm models (Langmuir model, Freundlich model and Temkin model) were used to fit the experimental data of the adsorption isotherm behavior of GCP at different rhenium concentrations. The solution volume was 50 mL, the pH of the solution was 4, and the applied voltage was 1.2 V. Adsorption isotherm curves were plotted.
[0065] like Figure 8 As shown, the nonlinear and linear experimental data fitting results for this material both show that the R-value of the Langmuir model is high. 2 The maximum value is 0.98, indicating that the adsorption process better conforms to the Langmuir model. Therefore, it is considered that the adsorption behavior of rhenium by the GCP composite electrode material as an adsorbent is monolayer adsorption, with a maximum saturation adsorption capacity of 297.08 mg·g⁻¹. -1 .
[0066] (vi) Infrared spectra of raw materials and aerogel GCP composite electrode materials before and after adsorption
[0067] Infrared spectral results as follows Figure 9 As shown, it is located at 3400cm -The broad peak around ¹ corresponds to the -OH stretching vibration, mainly originating from hydroxyl groups on the material surface or adsorbed water molecules. At 3200 cm⁻¹... - ¹-3500cm - A broad peak appears within the range ¹, attributed to the stretching vibration of -NH, at approximately 1500 cm⁻¹. - ¹ It has a CN stretching vibration peak at approximately 1300 cm⁻¹. - ¹, CN belonging to the doped aniline structure + Vibration, at approximately 1750cm - The absorption by the C=O stretching vibration of carboxylic acid within the range¹ disappears, followed by the appearance of the peak corresponding to polyaniline, indicating that ginger carboxymethyl cellulose and polyaniline are successfully bound. At 900 cm⁻¹ - ¹-1000cm - A new absorption peak appeared in region ¹, which is attributed to the stretching vibration of Re-O and is a perrhenate (ReO4) ion. - The typical characteristic absorption of Re is observed. This result directly proves the effective adsorption of Re by the aerogel GCP composite electrode material of the present invention, indicating that Re has been successfully bound and fixed on the surface of the aerogel GCP composite electrode material.
Claims
1. A GCP composite electrode material, characterized in that, The application discloses a gelatinous composite electrode material GCP.
2. The method for preparing an aerogel GCP composite electrode material according to claim 1, characterized in that, The preparation method comprises the following steps: 1) preparation of ginger carboxymethyl cellulose GCNF: uniformly mix citric acid, choline chloride and water to obtain a uniform transparent eutectic solvent, then add ginger powder, heat and stir, wash, and dry to obtain ginger carboxymethyl cellulose GCNF; 2) preparation of polyaniline: dissolve ammonium persulfate in hydrochloric acid, slowly drop the obtained solution into an aniline hydrochloride solution, continuously stir in an ice water bath, wash, and dry to obtain polyaniline PANI; 3) dissolve the ginger carboxymethyl cellulose GCNF in deionized water, dissolve the polyaniline PANI in hydrochloric acid, mix the GCNF aqueous solution and the PANI hydrochloride solution, uniformly stir, and freeze-dry to obtain the gelatinous composite electrode material GCP.
3. The method for preparing an aerogel GCP composite electrode material according to claim 2, characterized in that, In step 1), the mass ratio of citric acid, choline chloride and water is (5-7):(1.5-2.5):(1.5-2.5).
4. The method of claim 2, wherein the aerogel GCP composite electrode material is prepared by the steps of: In step 1), the heating temperature is 120-140 DEG C, and the stirring time is 3-4 h.
5. The method for preparing an aerogel GCP composite electrode material according to claim 2, characterized in that, In step 2), the mass ratio of ammonium persulfate and aniline is (1.0-1.5):
1.
6. The method of claim 2, wherein the aerogel GCP composite electrode material is prepared by the steps of: In step 3), the mass ratio of ginger carboxymethyl cellulose GCNF and polyaniline PANI is 1:(1-3).
7. The gelatinous composite electrode material GCP according to any one of claims 1-6 is applied to recovery of rhenium by electro-adsorption.
8. Use according to claim 7, characterized in that, The method is as follows: using a two-electrode electro-adsorption device, the gelatinous composite electrode material GCP is uniformly mixed with PVDF and conductive carbon black, a small amount of N-methyl pyrrolidone is added, and the mixture is uniformly mixed and coated on a carbon plate, and the electrode prepared after drying is used as an anode; a carbon rod is used as a cathode; rhenium-containing wastewater is used as an electrolyte, an external voltage is applied through a constant-voltage power supply, and Re(VII) in the solution is electro-adsorbed.
9. Use according to claim 8, characterized in that, The mass ratio of the gelatinous composite electrode material GCP, PVDF and conductive carbon black is (7-9):(0.5-1.5):(0.5-1.5); the drying temperature is 70-90 DEG C, and the drying time is 12-14 h.
10. Use according to claim 8, characterized in that, The pH of the rhenium-containing wastewater is adjusted to 1-5; the applied external voltage is 0.5-1.4 V; and the electro-adsorption time is 1-2 h.