CN115634669B - 3D mushroom waste aerogel, preparation method thereof and application thereof in adsorbing radionuclide technetium - Google Patents
3D mushroom waste aerogel, preparation method thereof and application thereof in adsorbing radionuclide technetium Download PDFInfo
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Abstract
The invention discloses a 3D mushroom waste aerogel, a preparation method thereof and application thereof in adsorbing radionuclide technetium. Extracting cellulose from mushroom waste, and winding with polyvinyl alcohol macromolecular chains under ultrasound. And then, carrying out organic modification by using 3-aminopropyl triethoxy silane to expose free amino, and finally, introducing schiff alkali bond with selectivity to technetium while crosslinking polyaminoimidazole ionic liquid by glutaraldehyde to synthesize the 3D gas gel-like mushroom waste adsorbing material 3D-MS. The present invention selects rhenium having a similar charge density and size to technetium for adsorption experiments. The 3D mushroom waste aerogel prepared by the invention has a wide adsorption range on technetium, and particularly has an adsorption capacity on rhenium of 206.41 mg.g at pH=4 ‑1 . The 3D-MS adsorbent prepared by the invention has high selective adsorptivity to technetium, realizes the treatment of waste by waste, and has strong application value.
Description
Technical Field
The invention belongs to the technical field of treatment of nuclide technetium and preparation of green adsorption materials, and particularly relates to a method for extracting cellulose from mushroom waste, and winding the cellulose with a polyvinyl alcohol macromolecular chain under the action of ultrasound. And then, carrying out organic modification on the mixture by using 3-aminopropyl triethoxysilane (APTES) to expose free amino, and finally, introducing schiff alkali bond with selectivity on technetium while crosslinking polyaminoimidazole ionic liquid by glutaraldehyde to synthesize the 3D gas gel mushroom waste adsorbing material 3D-MS.
Background
Technetium 99 Tc) is one of the most dangerous radioisotopes in nuclear waste, with a long half-life (t) 1/2 ＝2.13×10 5 yrs), nuclear fissionHigh yield, strong environmental fluidity, strong volatility in the process of vitrification of waste liquid, etc. Nuclear fission has produced about 400 metric tons since the first use of nuclear reactors 70 years ago 99 Tc。 99 Tc is mainly in a stable oxidation state (TcO) 4 - ) In the form of nuclear fuel waste water. TcO (TcO) 4 - Has high solubility (11.3 mol.L) -1 The water is extremely easy to spread on the surface layer of the crust, and forms a great threat to the water environment at 20 ℃. Furthermore, tcO 4 - The volatility and reducibility of (c) also severely affect the vitrification of the nuclear waste and uranium extraction processes. Therefore, the selective and effective fixation from nuclear waste and contaminated groundwater 99 Tc is of great significance. But because of the difficulty in handling TcOs with high radioactivity in the laboratory 4 - While ReO 4 - Is a kind of compound with TcO 4 - Structurally similar non-radioactive analogs, therefore, in the laboratory, reO 4 - Are often used to evaluate TcO 4 - Is not limited, and the removal effect of the catalyst is not limited.
In recent years, tcO was removed from aqueous solutions 4 - Various methods of (a) have been widely studied, such as solvent extraction, ion exchange, chemical precipitation, redox and adsorption methods. The adsorption method adsorbs target ions to the surface of the adsorbent by the action of molecular attraction or chemical bond force, so that the separation effect is realized. The adsorption method has the advantages of larger adsorption capacity, good regeneration performance and selectivity, environmental friendliness, quick kinetics, simple operation, low cost and the like, and is favored in a plurality of separation methods.
Cellulose has been attracting attention from many students as a natural macromolecular substance, and new materials developed based on cellulose have been developed in recent years. An aerogel is a gel that replaces the liquid in its porous structure with air, and the porous structure does not collapse during the replacement process. As a third generation aerogel, the cellulose-based aerogel has not only numerous advantages of the conventional silica aerogel and polymer aerogel but also fibers due to its low density, high porosity, large specific surface area, abundant three-dimensional porous structure and excellent thermal/electrical propertiesCharacteristics of the element itself, such as biocompatibility. The use of cellulose-based aerogels in environmental remediation, antibacterial agents, EMI shielding, and electrochemical energy storage has been lacking. The hydrophobic cellulose nanofiber aerogel prepared by Hasan. M can be used as super-adsorbent for resisting toxic textile dye such as crystal violet dye at 10mg.L -1 In the Crystal Violet (CV) aqueous solution, the adsorption capacity of the silane modified cellulose nanofiber aerogel is 150 mg.g -1 . Wei et al prepared a nanofiber carbon aerogel using bacterial cellulose, which has extremely strong adsorption capacity to the target antibiotics, such as 1926, 1264 and 525 mg.g of maximum adsorption capacity of para-norfloxacin, sulfamethoxazole and chloramphenicol, respectively -1 。
Disclosure of Invention
According to the invention, mushroom waste is used as a matrix, 3D aerogel is synthesized through crosslinking polyaminoimidazole ionic liquid, the treatment capacity of the aerogel on technetium is evaluated through researching the adsorption capacity of the aerogel on rhenium, and the stability and adsorption capacity of the aerogel synthesized under different proportion conditions are obtained through changing experimental conditions. Not only is beneficial to solving the pollution problem of biomass waste represented by mushroom waste, but also is beneficial to treating technetium pollution, thereby realizing the aim of treating waste by waste.
The invention is realized by the following technical scheme: a preparation method of the 3D mushroom waste aerogel comprises the following steps:
1) Grinding mushroom waste into powder, adding the powder into deionized water, stirring at room temperature to prepare suspension, adding 2, 6-tetramethylpiperidine oxide (TEMPO), sodium bromide and 9% sodium hypochlorite, adjusting the pH value of a mixed system to be 10 by sodium hydroxide or hydrochloric acid, performing ultrasonic dispersion, centrifuging, drying the obtained precipitate to obtain an intermediate product; grinding the intermediate product into powder, adding deionized water, uniformly mixing, adding a tertiary butanol solution of p-toluenesulfonic acid, uniformly mixing, and freeze-drying to obtain an intermediate;
2) Adding the intermediate obtained in the step 1) into deionized water, then adding a polyvinyl alcohol (PVA) solution, performing ultrasonic dispersion to prepare a macromolecule winding suspension, dropwise adding 3-aminopropyl triethoxysilane (APTES) under continuous stirring, heating to 80 ℃ and stirringAfter stirring for 2h, polyaminoimidazole ionic liquid (PIL-NH) was added 2 ) And (3) dropwise adding glutaraldehyde under stirring, continuously stirring for 2 hours, and freeze-drying to obtain the 3D mushroom waste aerogel.
Preferably, in step 1), the mushroom waste is ground into powder, sieved through a 200 mesh sieve, and the undersize is taken.
Preferably, in the step 1), the mass ratio of the intermediate product to the p-toluenesulfonic acid=1:0.05-0.2.
Preferably, in step 2), the intermediate is polyvinyl alcohol=1:0.5-4 in mass ratio.
Preferably, in step 2), 0 to 0.4mL of 3-aminopropyl triethoxysilane is added per 1mL of suspension.
Preferably, in step 2), 0 to 0.2g of polyaminoimidazole ionic liquid is added per 1mL of suspension.
Preferably, in step 2), 0 to 0.4mL glutaraldehyde is added per 1mL of suspension.
The invention provides an application of 3D mushroom waste aerogel serving as an adsorbent in adsorbing radionuclide technetium.
Preferably, the method is as follows: taking solution containing technetium ions, regulating the pH value of the solution to be 1-7, adding 3D mushroom waste aerogel, and heating at 30 ℃ for 180-200 r.min -1 And (3) vibrating and adsorbing for 24 hours, filtering and drying.
According to the invention, cellulose in mushroom waste is used for winding with polyvinyl alcohol, mushroom waste is hydrolyzed by APTES to enable the mushroom waste to have primary amino groups, and glutaraldehyde is used for crosslinking with polyaminoimidazole ionic liquid through aldol condensation to form the 3D aerogel-like material.
The beneficial effects of the invention are as follows:
1) The 3D mushroom waste aerogel contains a large amount of chloride ions which can exchange ions with technetium (rhenium) and C=N double bonds which can coordinate with the technetium (rhenium), and the polyaminoimidazole ionic liquid is crosslinked on a molecular chain formed by winding cellulose and polyvinyl alcohol through glutaraldehyde, so that the aerogel is formed.
2) The 3D mushroom waste aerogel prepared by the method is green and environment-friendly in synthesis path, and the synthesized aerogel adsorption material has the advantages of developed pores, stable structure, strong pressure resistance, good rebound resilience, large adsorption quantity of technetium (rhenium) element and practical applicability.
3) The invention has wide sources of raw materials, quick and efficient reaction, mild reaction conditions, capability of being carried out under the condition of water or oxygen, no need of expensive catalyst, and capability of being used for treating technetium element in water pollution.
4) The invention is not only beneficial to solving the pollution problem of biomass waste represented by waste mushroom waste, but also beneficial to recycling and utilizing radionuclide technetium, thereby achieving the purpose of treating waste by waste.
5) The 3D mushroom waste aerogel prepared by the invention has larger adsorption quantity to rhenium in solution in the pH=3-7 range, and the maximum adsorption quantity to rhenium is 260.41 mg.g when the pH=4 -1 。
In conclusion, the 3D mushroom waste aerogel prepared by the method can effectively adsorb rhenium ions, and the preparation process is simple, convenient and green, and the aerogel has the advantages of good rebound resilience, high adsorption rate, portability and practical practicability.
Drawings
FIG. 1 is a schematic representation of a polyaminoimidazole ionic liquid modified 3D mushroom waste aerogel synthesis.
FIG. 2 is a scanning electron microscope image of mushroom waste (A) and 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G) (B).
Fig. 3 is an infrared spectrum of a 3D mushroom waste aerogel.
Fig. 4 is a graph comparing adsorption performance of 3D mushroom waste aerogel to rhenium at ph=1-7 for materials of different synthesis conditions.
Fig. 5 is a graph of adsorption isotherms fit of 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G) to rhenium at ph=4.
FIG. 6 is the effect of different synthesis conditions on the adsorption capacity of the 3D mushroom waste aerogel.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the invention.
Example 1 3D mushroom waste aerogel prepared with different addition amounts of polyaminoimidazole Ionic liquids
1. 3D mushroom waste aerogel (3D-MS-0.2A-0 PIL-0.4G)
In this example, the mushroom waste is obtained from the waste material after planting mushrooms, and its main components are wood chips, wheat bran, gypsum and mushroom strains.
1) Grinding mushroom waste into powder with a pulverizer, sieving with a 200 mesh screen, collecting the undersize as mushroom waste powder, and marking as MS-200.
Adding 2.5g of mushroom waste powder MS-200 into 200mL of deionized water, stirring at room temperature for 2h to obtain suspension, adding 0.016g of 2, 6-tetramethylpiperidine oxide (TEMPO), 0.1g of sodium bromide and 10mL of sodium hypochlorite with concentration of 9%, and adding 0.5 mol.L -1 Sodium hydroxide or 0.5 mol.L -1 Repeatedly adjusting the pH value of the solution with hydrochloric acid to ensure that the pH value is kept unchanged=10, ultrasonically dispersing for 1h, centrifuging, washing the obtained precipitate twice with deionized water, and drying at 50 ℃ to obtain an intermediate product, namely c-MS.
2) The dried c-MS was weighed and ground to a powder, and 48mL of deionized water was added and mixed well. A further 0.1 times the mass of c-MS of TsOH (p-toluenesulfonic acid) was dissolved in 50mL of t-butanol. Mixing the two solutions, stirring for 5min, sealing with preservative film, freeze drying in refrigerator for 24 hr, and taking out to obtain intermediate, and marking as MS.
3) 0.1g of MS is added into 2mL of deionized water, then 1mL of polyvinyl alcohol solution (PVA) with the concentration of 0.05g/mL is added, and the mixture is dispersed for 1h by ultrasonic, so as to prepare a macromolecule winding suspension, and the suspension is marked as MS-PVA.
4) Taking 2mL of MS-PVA, dropwise adding 0.2mL of 3-aminopropyl triethoxysilane (APTES) under the stirring condition, heating to 80 ℃ and stirring for 2h, and adding 0g of polyaminoimidazole ionic liquid (PIL-NH) 2 ) After stirring for 30min, 0.4mL Glutaraldehyde (GA) is added dropwise, stirring is continued for 2h, and after stirring, the 3D mushroom waste aerogel is obtained by freeze drying, and is named as 3D-MS-0.2A-0PIL-0.4G.
2. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G)
Prepared as described in 1, except that 0.1g of polyaminoimidazole ion was usedLiquid (PIL-NH) 2 ) Substitution of 0g polyaminoimidazole ionic liquid (PIL-NH) in 1 2 ) Obtaining the 3D mushroom waste aerogel named as 3D-MS-0.2A-0.1PIL-0.4G.
3. 3D mushroom waste aerogel (3D-MS-0.2A-0.2 PIL-0.4G)
Prepared as described in 1, except that 0.2g of polyaminoimidazole ionic liquid (PIL-NH 2 ) Substitution of 0g polyaminoimidazole ionic liquid (PIL-NH) in 1 2 ) Obtaining the 3D mushroom waste aerogel named as 3D-MS-0.2A-0.2PIL-0.4G.
4. 3D mushroom waste aerogel (3D-MS-0.2A-0.3 PIL-0.4G)
Prepared as described in 1, except that 0.3g of polyaminoimidazole ionic liquid (PIL-NH 2 ) Substitution of 0g polyaminoimidazole ionic liquid (PIL-NH) in 1 2 ) Obtaining the 3D mushroom waste aerogel named as 3D-MS-0.2A-0.3PIL-0.4G.
5. 3D mushroom waste aerogel (3D-MS-0.2A-0.4 PIL-0.4G)
Prepared as described in 1, except that 0.4g of polyaminoimidazole ionic liquid (PIL-NH 2 ) Substitution of 0g polyaminoimidazole ionic liquid (PIL-NH) in 1 2 ) Obtaining the 3D mushroom waste aerogel named as 3D-MS-0.2A-0.4PIL-0.4G.
Example 2 3D mushroom waste aerogel prepared with different addition amounts of silane coupling Agent (APTES)
1. 3D mushroom waste aerogel (3D-MS-0A-0.2 PIL-0.4G)
In this example, the mushroom waste is obtained from the waste material after planting mushrooms, and its main components are wood chips, wheat bran, gypsum and mushroom strains.
1) Grinding mushroom waste into powder with a pulverizer, sieving with a 200 mesh screen, collecting the undersize as mushroom waste powder, and marking as MS-200.
Adding 2.5g of mushroom waste powder MS-200 into 200mL of deionized water, stirring at room temperature for 2h to obtain suspension, adding 0.016g of 2, 6-tetramethylpiperidine oxide (TEMPO), 0.1g of sodium bromide and 10mL of sodium hypochlorite with concentration of 9%, and adding 0.5 mol.L -1 Sodium hydroxide or 0.5 mol.L -1 Repeated adjustment of hydrochloric acidThe pH of the solution was kept constant at ph=10, after 1h of ultrasonic dispersion, centrifuged, washed twice with deionized water and the resulting precipitate was dried at 50 ℃ to give an intermediate, labeled c-MS.
2) The dried c-MS was weighed and ground to a powder, and 48mL of deionized water was added and mixed well. A further 0.1 times the mass of c-MS of TsOH (p-toluenesulfonic acid) was dissolved in 50mL of t-butanol. Mixing the two solutions, stirring for 5min, sealing with preservative film, freeze drying in refrigerator for 24 hr, and taking out to obtain intermediate, and marking as MS.
3) 0.1g of MS is added into 2mL of deionized water, then 1mL of polyvinyl alcohol solution (PVA) with the concentration of 0.05g/mL is added, and the mixture is dispersed for 1h by ultrasonic, so as to prepare a macromolecule winding suspension, and the suspension is marked as MS-PVA.
4) Taking 2mL of MS-PVA, dropwise adding 0mL of 3-aminopropyl triethoxysilane (APTES) under the stirring condition, heating to 80 ℃ and stirring for 2h, and adding 0.1g of polyaminoimidazole ionic liquid (PIL-NH) 2 ) After stirring for 30min, 0.4mL Glutaraldehyde (GA) is added dropwise, stirring is continued for 2h, and after stirring, the 3D mushroom waste aerogel is obtained by freeze drying, and is named as 3D-MS-0A-0.1PIL-0.4G.
2. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G)
The preparation was carried out as described in 1, except that 0.2mL of 3-aminopropyl triethoxysilane (APTES) was used instead of 0mL of 3-aminopropyl triethoxysilane (APTES) in 1 to obtain 3D mushroom waste aerogel, designated 3D-MS-0.2A-0.1PIL-0.4G.
3. 3D mushroom waste aerogel (3D-MS-0.4A-0.1 PIL-0.4G)
The preparation was carried out as described in 1, except that 0.4mL of 3-aminopropyl triethoxysilane (APTES) was used instead of 0mL of 3-aminopropyl triethoxysilane (APTES) in 1 to obtain 3D mushroom waste aerogel, designated 3D-MS-0.4A-0.1PIL-0.4G.
4. 3D mushroom waste aerogel (3D-MS-0.6A-0.1 PIL-0.4G)
The preparation was carried out as described in 1, except that 0.6mL of 3-aminopropyl triethoxysilane (APTES) was used instead of 0mL of 3-aminopropyl triethoxysilane (APTES) in 1 to obtain 3D mushroom waste aerogel, designated 3D-MS-0.6A-0.1PIL-0.4G.
5. 3D mushroom waste aerogel (3D-MS-0.8A-0.1 PIL-0.4G)
The preparation was carried out as described in 1, except that 0.8mL of 3-aminopropyl triethoxysilane (APTES) was used instead of 0mL of 3-aminopropyl triethoxysilane (APTES) in 1 to obtain 3D mushroom waste aerogel, designated 3D-MS-0.8A-0.1PIL-0.4G.
Example 3D mushroom waste aerogel prepared with different Glutaraldehyde (GA) addition amounts
1. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0G)
In this example, the mushroom waste is obtained from the waste material after planting mushrooms, and its main components are wood chips, wheat bran, gypsum and mushroom strains.
1) Grinding mushroom waste into powder with a pulverizer, sieving with a 200 mesh screen, collecting the undersize as mushroom waste powder, and marking as MS-200.
Adding 2.5g of mushroom waste powder MS-200 into 200mL of deionized water, stirring at room temperature for 2h to obtain suspension, adding 0.016g of 2, 6-tetramethylpiperidine oxide (TEMPO), 0.1g of sodium bromide and 10mL of sodium hypochlorite with concentration of 9%, and adding 0.5 mol.L -1 Sodium hydroxide or 0.5 mol.L -1 Repeatedly regulating pH value of the solution with hydrochloric acid to maintain pH=10, ultrasonically dispersing for 1 hr, centrifuging, washing twice with deionized water, taking out precipitate, drying at 50deg.C to obtain intermediate product, and marking as c-MS.
2) The dried c-MS was weighed and ground to a powder, and 48mL of deionized water was added and mixed well. A further 0.1 times the mass of c-MS of TsOH (p-toluenesulfonic acid) was dissolved in 50mL of t-butanol. Mixing the two solutions, stirring for 5min, sealing with preservative film, freeze drying in refrigerator for 24 hr, and taking out to obtain intermediate, and marking as MS.
3) 0.1g of MS is added into 2mL of deionized water, then 1mL of polyvinyl alcohol solution (PVA) with the concentration of 0.05g/mL is added, and the mixture is dispersed for 1h by ultrasonic, so as to prepare a macromolecule winding suspension, and the suspension is marked as MS-PVA.
4) Taking 2mL of MS-PVA, dropwise adding 0.2mL of 3-aminopropyl triethoxysilane (APTES) under the condition of stirring,stirring at 80deg.C for 2 hr, adding 0.1g polyaminoimidazole ionic liquid (PIL-NH) 2 ) Continuously stirring for 30min, dropwise adding 0mL Glutaraldehyde (GA), continuously stirring for 2h, and freeze-drying to obtain 3D mushroom waste aerogel named as 3D-MS-0.2A-0.1PIL-0G after stirring.
2. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.2G)
The preparation was carried out as described in 1, except that 0.2mL Glutaraldehyde (GA) was used instead of 0mL Glutaraldehyde (GA) in 1 to give a 3D mushroom waste aerogel, designated 3D-MS-0.2A-0.1PIL-0.2G.
3. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G)
The preparation was carried out as described in 1, except that 0.4mL Glutaraldehyde (GA) was used instead of 0mL Glutaraldehyde (GA) in 1 to give a 3D mushroom waste aerogel, designated 3D-MS-0.2A-0.1PIL-0.4G.
4. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.6G)
The preparation was carried out as described in 1, except that 0.6mL Glutaraldehyde (GA) was used instead of 0mL Glutaraldehyde (GA) in 1 to give a 3D mushroom waste aerogel, designated 3D-MS-0.2A-0.1PIL-0.6G.
5. 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.8G)
The preparation was carried out as described in 1, except that 0.8mL Glutaraldehyde (GA) was used instead of 0mL Glutaraldehyde (GA) in 1 to give a 3D mushroom waste aerogel, designated 3D-MS-0.2A-0.1PIL-0.8G.
Characterization of
1. FIG. 2 is a scanning electron microscope image of mushroom waste MS-200 (A) and 3D mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G) (B). As can be seen from fig. 2, although the components in the mushroom waste are relatively complex, it is not easy to see that the mushroom waste has an aggregation structure of short fibers, and the cross-linked aerogel has a loose porous structure, which indicates that the mushroom waste aerogel 3D-MS has a large pore structure capable of effectively transferring mass after being modified, in addition to the schiff base bond which is an effective group for adsorbing technetium (rhenium).
2. Fig. 3 is an infrared spectrum of a 3D mushroom waste aerogel. MS-200, 3D-MS-0.2A-0PIL-0.4G and 3D-MS-0.2A-0.1PIL-0.4G respectively represent mushroomsThe waste is ground, is sieved by a 200-mesh sieve, and is not added with the mushroom waste aerogel of the polyaminoimidazole ionic liquid, and the mushroom waste aerogel with the optimal proportion is obtained. As shown in FIG. 3 at 3300cm -1 Broad dispersion peaks appear in the vicinity MS-200, 3D-MS-0.2A-0PIL-0.4G and 3D-MS-0.2A-0.1PIL-0.4G, and the possible O-H stretching vibration peaks of cellulose and hydroxyl groups of polyvinyl alcohol in mushroom waste are caused, and after the polyaminoimidazole ionic liquid is crosslinked, N-H stretching vibration exists in free amino groups and can be overlapped. And either the C=N in schiff base or the skeleton characteristic peak of imidazole ring is overlapped with the cellulose characteristic absorption peak, thus the peak is in 1620cm -1 Has stronger absorption peak. As compared with MS-200, the 3D-MS-0.2A-0PIL-0.4G and 3D-MS-0.2A-0.1PIL-0.4G showed 1107cm -1 And 912cm -1 Two new peaks are formed by C-N bond stretching vibration and N-H out-of-plane deformation vibration respectively. It was concluded from this that the preparation of mushroom waste aerogel crosslinked by glutaraldehyde was successful. And for the optimum proportion of 3D-MS material, at 2342cm -1 A more pronounced new peak appears, which may be the c=n formed by successful condensation of the amino group with glutaraldehyde + The stretching vibration peak generated by H bond, but the 3D-MS-0.2A-0PIL-0.4G does not appear, probably due to the participation of the polyaminoimidazole ionic liquid in crosslinking, so that the amino content in the aerogel is increased. In summary, mushroom waste and polyaminoimidazole ionic liquids have been successfully crosslinked together by glutaraldehyde to form 3D-MS aerogels.
EXAMPLE 4 use of 3D Mushroom waste aerogel as adsorbent for the adsorption of radionuclide technetium
Adsorption effect of 3D mushroom waste aerogel on technetium (rhenium) at different acidity
The method comprises the following steps: 20mg of MS-200, 3D-MS-0A-0.1PIL-0.4G,3D-MS-0.2A-0PIL-0.4G,3D-MS-0.2A-0.1PIL-0G and 3D-MS-0.2A-0.1PIL-0.4G (abbreviated as MS-200, 0APTES, 0PIL, 0G and 3DMS, respectively) prepared in examples 1-3 were weighed, respectively, and 20mL was added at a concentration of 20mg L -1 Re (VII) solution, pH of the solution is 1, 2, 3, 4, 5, 6 and 7 respectively, and the solution is oscillated for 24 hours in an oscillation box at 30 ℃ and 180 r/min. The results are shown in FIG. 4.
As can be seen from fig. 4, untreated MS-200 has little adsorption capacity for rhenium; the material without APTES is characterized in that polyaminoimidazole ionic liquid and glutaraldehyde are subjected to aldol condensation, cellulose and glutaraldehyde are subjected to aldol condensation, the reaction rate is different, aerogel can not be formed, and the adsorption performance on rhenium is poor. However, without the addition of PIL, the schiff base c=n double bond formed by the reaction also has a higher selectivity for rhenium, especially at pH 3, with an adsorption rate for 20ppm rhenium even higher than 3DMS, since the cellulose is entangled with polyvinyl alcohol and then subjected to APTES treatment to expose the amino group, which is then subjected to aldol condensation with glutaraldehyde. The modified 3DMS not only has C=N double bonds formed by cellulose and glutaraldehyde, but also contains C=N double bonds formed by polyaminoimidazole ionic liquid and glutaraldehyde, and chloride ions in the polyaminoimidazole ionic liquid can exchange ions with rhenium ions, so that the modified 3DMS has more excellent adsorption capacity, namely, the adsorption capacity of 70% or more in the pH range of 3-7.
(II) adsorption effect of 3D-MS aerogel synthesized by different raw material proportion condition experiments on technetium (rhenium)
The method comprises the following steps: 20mg of all the adsorbent materials prepared in examples 1-3 were weighed out separately, and 20mL of 400mg L of pH=4 was added -1 Re (VII) solution was shaken in an shaking box at 30℃and 180r/min for 24h. The results are shown in FIG. 5.
As can be seen from FIG. 5, the adsorption of rhenium ions by the material gradually increased as the PIL content increased, and gradually decreased after the PIL content reached 0.1 g. APTES is used in an amount of 0.2mL (q= 215.08 mg.g) -1 ) In the case of the adsorption amount, the adsorption amount was lower than 0.8mL of APTES (q= 245.57 mg.g) -1 ) The mushroom waste aerogel was synthesized, but the performance of the aerogel was best at an APTES level of 0.2mL, both from the pressure resistance and resilience point of view. When the dosage of APTES and PIL is respectively fixed to be 0.2mL and 0.1g in experimental conditions, the increase of glutaraldehyde content can improve the adsorption performance of the material, and more aldehyde groups can be fully reacted with amino groups to generate schiff alkali when possible, so that the adsorption capacity of rhenium is higher. At the same time, the stability is reduced because fewer and fewer free amino groups weaken intermolecular hydrogen bonds in the aerogel. By a summary of the results of the experiments,the optimal synthesis proportion of the mushroom waste aerogel is determined by using 0.1g of mushroom waste, 0.4mL of glutaraldehyde, 0.2mL of APTES and 0.1g of polyaminoimidazole ionic liquid.
(III) adsorption isotherm of adsorption Re (VII) by mushroom waste aerogel (3D-MS-0.2A-0.1 PIL-0.4G) with optimal synthesis ratio
The method comprises the following steps: respectively taking 20mL with concentration of 20mg L -1 ，50mg L -1 ，80mg L -1 ，100mg L -1 ，150mg L -1 ，200mg L -1 ，400mg L -1 ，500mg L -1 ，600mg L -1 ，800mg L -1 Re (VII) solution, the pH was adjusted to 4. 20mg of 3D-MS-0.2A-0.1PIL-0.4G was added, respectively, and the mixture was oscillated in an oscillation tank at 30℃and 180r/min for 24 hours. The results are shown in FIG. 6.
From acidity experimental studies, it was found that 3D-MS-0.2A-0.1PIL-0.4G adsorption was best at ph=4, so that at ph=4, the saturated adsorption amount of aerogel was measured and experimental data were model fitted to Langmuir, freundlich, temkin, and Dubinin-Radushkevich adsorption isotherms. The fitting result is shown in FIG. 6, and the fitting values R of the four models 2 0.988,0.910,0.979,0.942 respectively. Thus, it was demonstrated that the adsorption isotherm of 3D-MS on Re (VII) more conforms to the Langmuir model, and the maximum adsorption amount on Re (VII) was 260.41 mg.g -1 This indicates that the adsorption of Re (VII) by the adsorption material is a monomolecular layer adsorption process, and the adsorption sites of the adsorbent are uniformly dispersed on the surface of the adsorbent.
(IV) elution effect of different resolving agents on rhenium-adsorbed mushroom waste aerogel
The method comprises the following steps: weighing 11 parts of 20mg 3D-MS-0.2A-0.1PIL-0.4G, adding 20mL of Re (VII) solution with pH=4 and concentration of 20ppm, placing into an oscillation box, setting the temperature at 30 ℃ and the rotating speed at 180 r.min -1 Shake for 24h. The solution was filtered and the adsorbed adsorbent was collected and dried. Each dried aerogel was added to 20mL of resolving fluid (HCl, HNO of different concentrations) 3 、NaCl、NH 4 SCN and NH 3 H 2 O), and after shaking at a constant temperature of 303K for 12 hours, the concentration of rhenium ions in the analysis solution was measured. The resolution was calculated and the results are shown in Table 1As shown.
TABLE 1 elution effect of different eluents on rhenium ions
As can be seen from Table 1, HCl and HNO 3 、NaCl、NH 4 SCN has good eluting effect on 3D-MS-0.2A-0.1PIL-0.4G, the eluting rate is higher than 90%, and HCl has the best eluting effect when the concentration is 1 mol.L -1 And 2 mol.L -1 The elution rate can reach 100.00 percent. Therefore, the 3D-MS has weak adsorption capacity on rhenium, is easy to elute, is favorable for recycling rhenium, and is a biological adsorption material with better application prospect.
Claims (6)
1. The 3D mushroom waste aerogel is characterized by comprising the following steps of:
1) Grinding mushroom waste into powder, adding into deionized water, stirring at room temperature to obtain suspension, adding 2, 6-tetramethylpiperidine oxide, sodium bromide and 9% sodium hypochlorite, adjusting pH of the mixed system to 10，Ultrasonic dispersion and centrifugation, and drying the obtained precipitate to obtain an intermediate product; grinding the intermediate product into powder, adding deionized water, uniformly mixing, adding a tertiary butanol solution of p-toluenesulfonic acid, uniformly mixing, and freeze-drying to obtain an intermediate;
2) Adding the intermediate obtained in the step 1) into deionized water, then adding a polyvinyl alcohol solution, and performing ultrasonic dispersion to prepare a suspension; dropwise adding 3-aminopropyl triethoxysilane under continuous stirring, heating to 80 ℃ and stirring for 2h, adding polyaminoimidazole ionic liquid, dropwise adding glutaraldehyde under stirring, continuously stirring for 2h, and freeze-drying to obtain 3D mushroom waste aerogel; adding 0.1-0.4 mL 3-aminopropyl triethoxysilane into each 1. 1mL suspension; 0.05 to 0.2. 0.2g polyaminoimidazole ionic liquid; 0.1 to 0.4. 0.4mL glutaraldehyde.
2. A 3D mushroom waste aerogel according to claim 1, wherein in step 1) the mushroom waste is ground into a powder, sieved through a 200 mesh screen and the undersize product is taken.
3. A 3D mushroom waste aerogel according to claim 1, wherein in step 1), the mass ratio of the intermediate product p-toluene sulfonic acid=1 is 0.05-0.2.
4. A 3D mushroom waste aerogel according to claim 1, wherein in step 2), the intermediate is polyvinyl alcohol=1, 0.5 to 4 in mass ratio.
5. Use of a 3D mushroom waste aerogel according to any of claims 1-4 as an adsorbent for adsorbing radionuclides technetium.
6. The use according to claim 5, characterized in that the method is as follows: taking solution containing technetium ions, regulating the pH value of the solution to be 1-7, adding 3D mushroom waste aerogel, and heating at 30 ℃ for 180-200 r min -1 Next, the mixture was subjected to vibration adsorption 24 and h, filtration and drying.
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| CN106517144A (en) * | 2016-11-15 | 2017-03-22 | 中国科学技术大学 | Method for preparing carbon nanofiber aerogel from wood |
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| CN106517144A (en) * | 2016-11-15 | 2017-03-22 | 中国科学技术大学 | Method for preparing carbon nanofiber aerogel from wood |
| CN108993434A (en) * | 2018-09-06 | 2018-12-14 | 潘钕 | A kind of preparation method of bagasse cellulose base weight metal ion adsorbent |
| CN109092265A (en) * | 2018-09-10 | 2018-12-28 | 陕西科技大学 | A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified |
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