CN113816473B - Method for combining mushroom stick-based conductive composite aerogel with electro-enhanced adsorption Re (VII) - Google Patents
Method for combining mushroom stick-based conductive composite aerogel with electro-enhanced adsorption Re (VII) Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0095—Preparation of aerosols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a method for combining mushroom rod based conductive composite aerogel with electric enhancement adsorption Re (VII). And preparing the mushroom stick base conductive composite aerogel by taking the waste mushroom sticks as raw materials. The prepared mushroom stick-based conductive composite aerogel is used as a working electrode, and Re (VII) is subjected to electric enhancement adsorption under the voltage of 0.8-1.2V. At an initial concentration of 300 mg.L ‑1 When the adsorption amount of the working electrode was 708 mg.g ‑1 The adsorption amount is significantly higher than that of static adsorption. Further adopting Langmuir adsorption isothermal model to fit the experimental data to obtain the maximum electric enhancement adsorption capacity of 942 mg.g for Re (VII) ‑1 Is 3.58 times of the traditional adsorption capacity. After three cycles of analysis and adsorption, the electro-adsorption capacity of the mushroom rod based conductive composite aerogel electrode to Re (VII) is stable, which indicates that the mushroom rod based conductive composite aerogel has good renewable performance.
Description
Technical Field
The invention belongs to the technical field of scattered metal adsorption, and particularly relates to an electric enhancement adsorption method of Re (VII) by mushroom-rod-based conductive composite aerogel.
Background
Rhenium is one of the rare elements in the crust, with an average crust abundance of about 0.4X10 -9 . Rhenium has no separate rhenium bed of industrial value, and industrial rhenium is derived primarily from molybdenum ores, copper-molybdenum ores, and rhenium produced in super-bedrock with platinum group element deposits. Currently, the world has ascertained that the rhenium reserves are about 2500t and the annual rhenium yield is about 50t. Rhenium resources in China are not abundant, and followWith the development of scientific technology, rhenium resources are increasingly scarce.
At present, the traditional method for recovering rare metals is numerous, but has advantages and disadvantages. Among them, the solvent extraction method has large extraction amount and lower process cost, but is volatile, has large toxicity and has serious pollution to the environment. The ion exchange method has the advantages of high separation rate, environment friendliness and easiness in recovery, but is high in price and long in process flow, so that the application is limited. The chemical precipitation method has simple and convenient operation process, but the smelting waste liquid generally contains impurity metal with higher concentration, so that the selectivity to rhenium is affected, and the separation effect is reduced. The adsorption method is widely applied to enrichment of Re (VII) due to the characteristics of convenient operation and the like, however, as adsorption is carried out, the concentration difference between the surface of the adsorbent and ions in the solution becomes smaller, the adsorption rate is slowed down, and the adsorption performance is further affected.
The mushroom stick refers to a mushroom stick after mushroom is planted. In general, after mushroom cultivation, the mushroom sticks are discarded, so that resource waste is caused.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for combining the mushroom rod-based conductive composite aerogel with good Re (VII) adsorption performance with the electric enhancement adsorption of Re (VII).
The technical scheme adopted by the invention is as follows: a method for combining mushroom stick based conductive composite aerogel with electro-enhanced adsorption Re (VII), comprising the following steps:
1) Preparation of working electrode: grinding the mushroom rod-based conductive composite aerogel, mixing the obtained mushroom rod-based conductive composite aerogel powder with conductive carbon black and polyvinylidene fluoride, adding a solvent for ultrasonic dispersion after fully grinding and uniformly mixing, uniformly coating the obtained uniformly mixed slurry on conductive carbon paper, and drying to obtain a mushroom rod-based conductive composite aerogel electrode serving as a working electrode;
2) The working electrode is taken as an anode, the graphite paper is taken as a cathode, the working electrode and the graphite paper are placed in an electric adsorption tank, and working voltage is applied;
3) Adsorption: the solution containing Re (VII) flows into the electro-adsorption cell from the negative electrode end, and flows out from the positive electrode end for adsorption.
Further, in the above method, in step 1), grinding the mushroom-rod-based conductive composite aerogel, sieving with a 200 mesh sieve, and taking the undersize as mushroom-rod-based conductive composite aerogel powder; according to the mass ratio, the mushroom stick based conductive composite aerogel powder comprises conductive carbon black and polyvinylidene fluoride=6:3:1-5:4:1.
Further, in the above method, in step 1), the solvent is N-methylpyrrolidone.
Further, in the above method, in step 2), the operating voltage is 0.8 to 1.2V.
Further, in the above method, in the step 3), the initial concentration of the Re (VII) -containing solution is adjusted to 100 to 300 mg.L -1 The pH is 2-4; controlling the flow rate of the Re (VII) -containing solution to be 25-50 mL.min -1 。
Further, the method comprises 4) analyzing: after saturated adsorption of the working electrode, the solution containing Re (VII) is replaced by an analysis solution, the working electrode is connected with the negative electrode by reverse connection with a power supply, graphite paper is connected with the positive electrode, and Re (VII) adsorbed on the working electrode is analyzed.
Further, in the above method, the analytical solution is 2 mol.L -1 Is a HCl of (C).
Further, according to the method, the preparation method of the mushroom-rod-based conductive composite aerogel comprises the following steps:
1) Preparation of intermediate CNF: pulverizing waste mushroom stick, sieving with 200 mesh sieve, collecting the sieved material to obtain mushroom stick powder, adding 10g mushroom stick powder into 70mL of powder with concentration of 3mol.L -1 Is 6 mol.L in concentration of 30mL and citric acid -1 In the hydrochloric acid mixture, under stirring, reacting for 3 hours at 70 ℃, then adding 500mL of deionized water to quench the reaction, adjusting the pH=7 of the reaction product by ammonia water, centrifugally washing to obtain a supernatant which is colorless, and drying to obtain an intermediate CNF;
2) Preparation of polyaniline nanofiber PANI: dissolving 0.292mL of aniline in 10mL of dichloromethane to obtain an oil phase; 0.1824g ammonium persulfate was dissolved in 10mL of 1 mol.L -1 Obtaining a water phase in the hydrochloric acid solution of (2); slowly transferring the aqueous phase into the oil phase at a transfer rate of 100s·mL -1 Reacting for 12 hours at 0 ℃, carrying out suction filtration, washing to be neutral by using absolute methanol and deionized water in sequence, and drying to obtain polyaniline nanofiber PANI;
3) Preparation of nanocomposite fiber suspension: adding deionized water into the intermediate CNF, and performing ultrasonic dispersion for 2 hours to obtain CNF gel with the mass percentage concentration of 2.0%; adding deionized water into polyaniline nanofiber PANI, and performing ultrasonic dispersion to obtain PANI suspension with the mass percentage concentration of 10%; mixing CNF gel and PANI suspension according to a mass ratio of 1:1, and performing ultrasonic treatment at room temperature for 30-60min to obtain nano composite fiber suspension;
4) Preparation of mushroom stick based conductive composite aerogel: freezing the obtained nano composite fiber suspension at-30deg.C for one night, and then placing into a vacuum freeze dryer for freezing for 48h to obtain the mushroom stick base conductive composite aerogel.
The beneficial effects of the invention are as follows:
1. in the invention, the electric enhancement adsorption utilizes a capacitive deionization technology, mushroom-rod-based conductive composite aerogel is used as a working electrode, and working voltage is applied for electric enhancement cooperative adsorption. During physical adsorption and chemical adsorption, re (VII) is adsorbed on the surface of the working electrode more rapidly and efficiently by applying working potential, and the adsorption capacity and adsorption rate of Re (VII) are enhanced.
2. In the invention, as the externally applied working voltage increases, the adsorption quantity gradually increases, and the adsorption rate is faster. Even at the lowest operating voltage of 0.8V, the adsorption amount of 90min is much higher than the saturated adsorption amount at the conventional adsorption, and the adsorption amount reaches the maximum value at 1.2V. The higher the operating voltage applied to the conductive aerogel electrode, the higher its adsorption performance to Re (VII) within a suitable operating voltage range.
3. In the invention, after three cycles of analysis and adsorption, the suction capacity of the mushroom rod-based conductive composite aerogel electrode to Re (VII) is slightly changed, and the mushroom rod-based conductive composite aerogel electrode still has good adsorption performance.
4. The electrochemical adsorption method has great advantages for ion capturing and releasing, and provides a brand-new exploration idea for enriching and recovering Re (VII) in the solution by the mushroom-rod-based conductive composite aerogel.
5. The invention has the advantages of low energy consumption, environmental protection, easy regeneration and the like, is favorable for developing a clean process for efficiently extracting the rare-earth element rhenium, simplifies the original production process, saves resources and energy sources, and has important scientific significance and practical application prospect.
Drawings
FIG. 1 is a schematic illustration of an electro-adsorption experiment of a mushroom stick based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII).
FIG. 2 is the effect of applied voltage on the performance of mushroom rod based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII).
FIG. 3 is the effect of acidity on the performance of mushroom stick based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII).
FIG. 4 is the effect of system flow rate mushroom stick based conductive composite aerogel in combination with electrically enhanced adsorption Re (VII) performance.
FIG. 5 is the effect of initial concentration on the performance of mushroom rod based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII).
FIG. 6 is a graph showing the effect of cycle number on the adsorption amount during the Re (VII) electro-adsorption.
Detailed Description
The invention is further illustrated by, but not limited to, the following specific examples.
Example 1 Mushroom rod based conductive composite aerogel
The preparation method comprises the following steps:
1. preparation of intermediate CNF
Pulverizing the waste mushroom sticks, sieving with a 200-mesh sieve, and taking the undersize to obtain mushroom stick powder. 10g of mushroom stick powder is added into 70mL of 3 mol.L -1 Is 6 mol.L in concentration of 30mL and citric acid -1 In the hydrochloric acid mixture of (2), the Fischer esterification reaction is carried out under the mechanical stirring at 800rpm, the reaction is carried out for 3 hours at 70 ℃, then 500mL of deionized water is added for quenching the reaction, ammonia water is used for adjusting the pH=7 of the reaction product, the supernatant is washed by centrifugation for a plurality of times to be colorless, and the intermediate CNF is obtained by drying.
2. Preparation of polyaniline nanofiber PANI
0.292mL of aniline was dissolved in 10mL of methylene chloride to give an oil phase. 0.1824g ammonium persulfate was dissolved in 10mL of 1 mol.L -1 To obtain an aqueous phase. Slowly transferring the water phase into the oil phase at a transfer rate of 100 s.mL -1 Reacting at 0deg.C for 12h, vacuum filtering, washing with anhydrous methanol and deionized water sequentially to neutrality, and oven drying to obtain polyaniline nanofiber (PANI)
3. Preparation of nanocomposite fiber suspensions
Adding deionized water into the intermediate CNF, and performing ultrasonic dispersion for 2 hours to obtain CNF gel with the mass percentage concentration of 2.0%. Deionized water is added into polyaniline nanofiber PANI, and PANI suspension with the mass percent concentration of 10% is obtained through ultrasonic dispersion. Mixing CNF gel and PANI suspension according to a mass ratio of 1:1, and performing ultrasonic treatment at room temperature for 30-60min to obtain nano composite fiber suspension.
4. Preparation of mushroom stick base conductive composite aerogel
Freezing the obtained nano composite fiber suspension at-30deg.C for one night, and then placing into a vacuum freeze dryer for freezing for 48h to obtain the mushroom stick base conductive composite aerogel.
Example 2A method of Mushroom rod based conductive composite aerogel in combination with electro-enhanced adsorption of Re (VII)
The working electrode was prepared using the mushroom-rod based conductive composite aerogel prepared in example 1, comprising the steps of:
1. preparation of working electrode
Grinding the mushroom-stick-based conductive composite aerogel, sieving with a 200-mesh sieve, and taking out the undersize to obtain the mushroom-stick-based conductive composite aerogel powder.
According to the mass ratio, the mushroom stick based conductive composite aerogel powder comprises conductive carbon black and polyvinylidene fluoride=6:3:1, the mushroom stick based conductive composite aerogel powder, the conductive carbon black and the polyvinylidene fluoride are mixed, fully ground and uniformly mixed, and the ratio of the feed to the liquid is 1g: adding solvent N-methyl pyrrolidone into 10ml, and performing ultrasonic dispersion to obtain slurry. And uniformly coating the obtained slurry on conductive carbon paper, and drying at 80 ℃ for 24-48 hours to obtain the mushroom-rod-based conductive composite aerogel electrode serving as the working electrode (1).
2. Electrode mounting
As shown in fig. 1, a working electrode (1) and graphite paper (2) are arranged in an electric adsorption tank (4), the working electrode (1) is connected with the positive electrode of a direct current power supply (3), the graphite paper (2) is connected with the negative electrode of the direct current power supply (3), a solution containing Re (VII) is filled in a liquid storage tank (5), the solution containing Re (VII) in the liquid storage tank (5) flows through a peristaltic pump (7) through a water inlet pipe (6) and then enters the electric adsorption tank (4) from the negative electrode end of the electric adsorption tank (4), after sequentially flowing through the graphite paper (2) and the working electrode (1), the solution flows out from the positive electrode end in the electric adsorption tank (4) and flows back into a liquid storage tank (5) through a water return pipe (8), the pH value of the reflux liquid is measured through a pH detector (9), and the concentration of Re (VII) is measured through an ultraviolet spectrophotometer (10). Wherein the effective adsorption area of the working electrode (1) is about 9cm 2 The spacing between the positive electrode plate and the negative electrode plate is 10mm. Preferably, an anion exchange membrane (11) is placed between the electroadsorption cell (4) and the working electrode (1) to help to better electrically enhance Re (VII) in the adsorption solution.
3. Adsorption of
Regulating the initial concentration of the Re (VII) -containing solution to be 100-300 mg.L -1 The pH is 2-4. Controlling the flow rate of the Re (VII) -containing solution to be 25-50 mL.min -1 . Applying a working voltage of 0.8-1.2V to the working electrode (1) and the graphite paper (2); the Re (VII) is adsorbed by the mushroom-rod-based conductive composite aerogel when the solution containing Re (VII) passes through the working electrode, and the solution is circulated in this way and is adsorbed for 90 minutes.
4. Resolution
After the working electrode (1) is saturated and adsorbed, the solution containing Re (VII) in the liquid storage tank (5) is replaced by analysis liquid, and the analysis liquid is reversely connected with a power supply, namely, the working electrode is connected with the negative electrode of a direct current power supply, the graphite paper is connected with the positive electrode of the direct current power supply, and the Re (VII) adsorbed on the working electrode is analyzed.
(one) Effect of applied voltage on the Performance of Mushroom rod based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII)
The method comprises the following steps: the initial concentration of the Re (VII) -containing solution in the reservoir was 100 mg.L -1 Ph=4, controlling the flow rate of the Re (VII) -containing solution to 25ml·min -1 . Respectively adjusting the working voltage between the positive electrode and the negative electrode to be 0V,0.8V,1.0V and 1.2V; at the temperature of 298K, the temperature,and (5) carrying out adsorption for 90min. Samples were taken every 1, 3, 5, 10, 15, 20, 30, 60, 90min, and the concentration of metallic rhenium in the samples was determined by ultraviolet spectrophotometry. The results are shown in FIG. 2.
As can be seen from FIG. 2, when the operating voltage of the system is 0V, i.e., the open circuit is established, the adsorption amount of rhenium by the positive electrode is only 77.08 mg.g at 90min -1 With the increase of the externally applied working voltage, the adsorption capacity is gradually increased, the adsorption rate is faster, the adsorption capacity for 90min is far higher than the saturated adsorption capacity under the conventional adsorption even under the lowest working voltage of 0.8V, the adsorption capacity reaches the maximum value under the condition of 1.2V, and the maximum value can reach 225 mg.g -1 . It can be seen that the higher the operating voltage applied to the composite conductive aerogel electrode, the higher its adsorption performance to Re (VII) within the appropriate operating voltage range.
(II) Effect of acidity on the Performance of Mushroom rod-based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII)
The method comprises the following steps: the initial concentration of the Re (VII) -containing solution in the reservoir was 100 mg.L -1 The ph=1, 2, and 4 of the solution was adjusted, and the flow rate of the Re (VII) -containing solution was controlled to 25ml·min -1 . Adjusting the working voltage between the positive electrode and the negative electrode to be 1.2V; adsorption was performed for 90min at 298K. Samples were taken every 1, 3, 5, 10, 15, 20, 30, 60, 90min, and the concentration of metallic rhenium in the samples was determined by ultraviolet spectrophotometry. The results are shown in FIG. 3.
As can be seen from FIG. 3, under the condition of applying electric potential, the adsorption amount of the mushroom-rod-based conductive composite aerogel to Re (VII) is highest at pH=4 and can reach 225 mg.g -1 The adsorption amount at ph=1 was 94.5mg·g -1 Still significantly higher than the amount of adsorption when no operating voltage is applied.
(III) Effect of System flow Rate on Performance of Mushroom rod based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII)
The method comprises the following steps: the initial concentration of the Re (VII) -containing solution in the reservoir was 100 mg.L -1 The pH=4 of the solution was adjusted, and the flow rate of the solution containing Re (VII) was controlled to 25 mL/min -1 And 50mL min -1 Adjusting the working voltage between the positive electrode and the negative electrode to be 1.2V; at a temperature of 298KAdsorption was carried out for 90min. Samples were taken every 1, 3, 5, 10, 15, 20, 30, 60, 90min, and the concentration of metallic rhenium in the samples was determined by ultraviolet spectrophotometry. The results are shown in FIG. 4.
As can be seen from FIG. 4, the flow rate was 25mL min -1 And 50mL min -1 Next, the adsorption amounts at 90 minutes were 225 mg.g, respectively -1 And 205 mg.g -1 。25mL·min -1 The adsorption rate and adsorption capacity are slightly higher than 50 mL.min -1 . The reasons are as follows: at 25 mL/min -1 At low flow rate, re (VII) has sufficient time to contact with the mushroom-rod-based conductive composite aerogel electrode, and at high flow rate, ions in the solution are not yet available to enter into the pore canal inside the electrode, so that the ions directly flow out of the system along with water flow without being adsorbed on the surface of the electrode, re (VII) just adsorbed on the surface of the electrode is easily taken away by high-speed water flow, and the adsorption quantity is reduced. The aerogel electrode material and the capacitive deionization adsorption system can realize good adsorption Re (VII) at high flow rate, so that the cost can be greatly reduced, and the capacitive deionization adsorption system has industrial application prospect.
(IV) Effect of initial concentration on Performance of Mushroom rod-based conductive composite aerogel in combination with electro-enhanced adsorption Re (VII)
The method comprises the following steps: the initial concentration of Re (VII) -containing solution in the reservoir was adjusted to be 100 mg.L -1 、200mg·L -1 、300mg·L -1 The pH=4 of the solution was adjusted, and the flow rate of the solution containing Re (VII) was controlled to 25 mL/min -1 Adjusting the working voltage between the positive electrode and the negative electrode to be 1.2V; after adsorption for 90min at 298K, samples were taken and the concentration of metallic rhenium in the samples taken was determined by UV spectrophotometry. The results are shown in FIG. 5.
As can be seen from fig. 5, as the initial Re (VII) solution concentration increases, the adsorption capacity thereof increases significantly. When the initial concentration is 300 mg.L -1 When the adsorption capacity of the mushroom stick based conductive composite aerogel electrode is 708 mg.g -1 The adsorption amount is significantly higher than that of static adsorption. Further fitting the experimental data by adopting a Langmuir adsorption isothermal model to obtain 942 mg.g of the maximum adsorption capacity of the mushroom rod-based conductive composite aerogel on Re (VII) -1 Is 3.58 times of static adsorption. Illustrating that the active sites for adsorption are uniformly distributed on the surface of the adsorbent for ReO 4 - Is the same, reO 4 - Uniformly adsorbing on the surface of the conductive aerogel to form monomolecular layer adsorption. The high adsorption quantity benefits from the rich functional groups contained in the PANI, and the hierarchical porous structure of the aerogel promotes the transmission of electrons and ions, so that the aerogel electrode has excellent capacitance performance, and the adsorption capacity is greatly improved.
And (V) an adsorption-desorption cycle experiment of the mushroom stick-based conductive composite aerogel on Re (VII) in combination with electric enhancement.
The method comprises the following steps: regulating the initial concentration of Re (VII) -containing solution in the reservoir to 100 mg.L -1 Ph=4, controlling the flow rate of the Re (VII) -containing solution to 25ml·min -1 Adjusting the working voltage between the positive electrode and the negative electrode to be 1.2V; after adsorption for 90min at 298K, the concentration of rhenium in the sample was determined by ultraviolet spectrophotometry and the adsorption amount was calculated.
After the adsorption is finished, the electric adsorption cell (4) is repeatedly washed by deionized water until the electric adsorption cell is neutral.
Then the working electrode is connected with the negative electrode of the direct current power supply (3) in a reverse way, the graphite paper is connected with the positive electrode of the direct current power supply (3), different desorption liquids shown in the table 1 are respectively filled in the liquid storage tank (5), and the flow speed of the desorption liquids is controlled to be 25 mL.min -1 The working voltage between the positive electrode and the negative electrode is 1.2V; the Re (VII) adsorbed on the working electrode was resolved for 1h at temperature 298K.
The above test was repeated and repeated for a plurality of adsorption-desorption cycle tests. The concentration of metallic rhenium was determined by ultraviolet spectrophotometry. The results are shown in Table 1 and FIG. 6.
TABLE 1 elution effect of different analysis solutions on rhenium ions
As is clear from Table 1, the concentration was 2 mol.L -1 Mushroom stick adsorbing rhenium by HCl pairThe analysis effect of the base conductive composite aerogel is best, and the analysis rate can reach 98.23%.
As can be seen from fig. 6, after three cycles, the suction capacity of the mushroom-rod based conductive composite aerogel electrode varies little to Re (VII), indicating that the mushroom-rod based conductive composite aerogel has good reproducibility.
Claims (7)
1. A method for combining mushroom stick based conductive composite aerogel with electro-enhanced adsorption Re (VII), which is characterized by comprising the following steps:
1) Preparation of working electrode: grinding the mushroom rod-based conductive composite aerogel, mixing the obtained mushroom rod-based conductive composite aerogel powder with conductive carbon black and polyvinylidene fluoride, adding a solvent for ultrasonic dispersion after fully grinding and uniformly mixing, uniformly coating the obtained uniformly mixed slurry on conductive carbon paper, and drying to obtain a mushroom rod-based conductive composite aerogel electrode serving as a working electrode;
2) The working electrode is taken as an anode, the graphite paper is taken as a cathode, the working electrode and the graphite paper are placed in an electric adsorption tank, and working voltage is applied;
3) Adsorption: the solution containing Re (VII) flows into the electro-adsorption cell from the negative electrode end, and flows out from the positive electrode end for adsorption;
the preparation method of the mushroom stick base conductive composite aerogel comprises the following steps:
1) Preparation of intermediate CNF: pulverizing waste mushroom stick, sieving with 200 mesh sieve, collecting the sieved material to obtain mushroom stick powder, adding 10g mushroom stick powder into 70mL concentration 3 mol.L -1 Is 6 mol.L in concentration with 30mL -1 In the hydrochloric acid mixture of (2), under stirring, reacting at 70 ℃ for 3h, then adding 500mL deionized water to quench the reaction, adjusting the pH=7 of the reaction product by ammonia water, centrifugally washing to obtain a supernatant which is colorless, and drying to obtain an intermediate CNF;
2) Preparation of polyaniline nanofiber PANI: dissolving 0.292mL aniline in 10mL dichloromethane to obtain an oil phase; 0.1824g ammonium persulfate was dissolved in 10mL at a concentration of 1 mol.L -1 Obtaining a water phase in the hydrochloric acid solution of (2); slowly transferring the water phase into the oil phase at a transfer rate of100 s·mL -1 Reacting at 0 ℃ for 12h, carrying out suction filtration, washing with absolute methanol and deionized water to be neutral in sequence, and drying to obtain polyaniline nanofiber PANI;
3) Preparation of nanocomposite fiber suspension: adding deionized water into the intermediate CNF, and performing ultrasonic dispersion on the mixture for 2h to obtain CNF gel with the mass percentage concentration of 2.0%; adding deionized water into polyaniline nanofiber PANI, and performing ultrasonic dispersion to obtain PANI suspension with the mass percentage concentration of 10%; mixing CNF gel and PANI suspension according to a mass ratio of 1:1, and performing ultrasonic treatment at room temperature for 30-60min to obtain nano composite fiber suspension;
4) Preparation of mushroom stick based conductive composite aerogel: freezing the obtained nano composite fiber suspension at-30deg.C overnight, and then placing into a vacuum freeze dryer for freezing 48 and h to obtain the mushroom stick base conductive composite aerogel.
2. The method according to claim 1, characterized in that: in the step 1), grinding the mushroom-stick-based conductive composite aerogel, sieving with a 200-mesh sieve, and taking the undersize as mushroom-stick-based conductive composite aerogel powder; according to the mass ratio, the mushroom stick based conductive composite aerogel powder comprises conductive carbon black and polyvinylidene fluoride=6:3:1-5:4:1.
3. The method according to claim 1, characterized in that: in the step 1), the solvent is N-methyl pyrrolidone.
4. The method according to claim 1, characterized in that: in the step 2), the working voltage is 0.8-1.2V.
5. The method according to claim 1, characterized in that: in step 3), the initial concentration of the Re (VII) -containing solution is adjusted to 100-300 mg.L -1 The pH is 2-4; controlling the flow rate of the Re (VII) -containing solution to be 25-mL.min -1 。
6. The method according to claim 1, characterized in that: comprising, 4) parsing: after saturated adsorption of the working electrode, the solution containing Re (VII) is replaced by an analysis solution, the working electrode is connected with a negative electrode by reverse connection with a power supply, graphite paper is connected with a positive electrode, and Re (VII) adsorbed on the working electrode is analyzed.
7. The method according to claim 6, wherein: the resolving fluid is 2 mol.L -1 Is a HCl of (C).
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| CN109776851A (en) * | 2019-01-04 | 2019-05-21 | 浙江工业大学 | A kind of bacteria cellulose/metal sulfide plural gel and preparation method thereof and conductive processing method |
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