CN115433387A - Method for preparing hydrophobic aerogel by using agaric fungus residues - Google Patents
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Abstract
The invention discloses a method for preparing hydrophobic aerogel by using agaric fungus residues, which takes waste agaric fungus residues as raw materials, removes lignin, hemicellulose and other impurities, and extracts cellulose and H in the fungus residues 2 SO 4 Hydrolyzing to obtain nano-cellulose, taking BmimCl (1-butyl-3-methylimidazolium chloride) ionic liquid as a nano-cellulose dissolving system, MTMS (methyl trimethoxy silane) modified nano-cellulose and MBA (N, N-methylene acrylamide) as cross-linkingThe preparation, combined with chemical crosslinking and freeze-drying technology, has a density of 47.002mg/cm 3 Ultra-light aerogel with porosity of 97.044%. The density of the aerogel tends to increase, and the porosity tends to be opposite to the density, and gradually decreases with the increase of the content of the nanocellulose. The cross lapped nano cellulose fibers with the net-shaped structure formed on the surface of the aerogel have good hydrophobic effect and can keep floating on the water surface for a long time.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for preparing hydrophobic aerogel by using agaric fungus residues.
Background
The cellulose is used as the most abundant renewable resource in the nature, has wide source and low price, and is a friendly material for preparing the functional aerogel adsorbent. Due to good biodegradability and biocompatibility, the composite material is widely applied to materials such as paper making, coatings, composite materials and aerogel. The agaric mushroom dregs are agricultural wastes derived from natural materials such as wood, straws and the like, and the cell walls of green plants are damaged after planting, so that the wood structure in the residual mushroom dregs becomes loose, and cellulose is easily extracted.
The aerogel has the characteristics of high porosity, low density, large specific surface area and the like, is a lightweight porous material with a three-dimensional network structure, has the rapid development of aerogel material preparation technology, introduces different functional groups through surface modification, or introduces cellulose materials, graphene and SiO 2 And the like, so that the functional application of the aerogel is promoted. Cellulose is as natural macromolecular compound, have that the reserve is big, wide distribution, characteristics such as can circulate regeneration, the unique molecular structure of cellulose makes it use extensively in the aspect of preparing ultralight cellulose aerogel, the intermolecular and intramolecular hydrogen bond effort can be formed to a large amount of hydroxyls of cellulose molecule chain end when dissolving regeneration shaping, the gel cross-linking strength has been improved, mechanical strength that can improve the aerogel through modifying cellulose, the excellent performance of oneself has been merged into in the time of possessing traditional aerogel characteristic, have extensive using meaning in purification printing and dyeing wastewater, water oil separating field.
In recent years, with the continuous expansion of the agaric industrial chain in China, agricultural and sideline products are gradually increased, the recycling of fungus residue waste becomes more and more important, and the new technology is adopted to prepare a new material with special performance and high added value. As a raw material with high cellulose content, the cellulose in the residual fungus dregs after planting the agaric is easy to extract, and the aerogel adsorption material with strong adsorption effect can be prepared by modification, pyrolysis or mixing.
Disclosure of Invention
In order to improve the resource utilization technology of the waste mushroom dregs and reduce the environmental pollution, the invention aims to provide the method for preparing the hydrophobic aerogel by using the agaric mushroom dregs, which solves the defects of low secondary utilization rate and resource waste of the waste mushroom dregs, is simple to operate, consumes less time and improves the resource conversion rate of the waste mushroom dregs.
In order to achieve the purpose, the invention adopts the technical scheme that the method for preparing the hydrophobic aerogel by using the agaric fungi residues comprises the following steps:
step 1, preparing nano-cellulose by an acidolysis method: the agaric residue is first pretreated with benzene and alcohol organic solvent and then treated with NaOH and NaClO 2 The solution is washed by alkali and bleached to purify the cellulose, and the obtained cellulose is mixed with H 2 SO 4 Uniformly mixing the solution, fully reacting, washing to be neutral, and freeze-drying to obtain nano-cellulose;
step 2, dissolving nano-cellulose: mixing the nano-cellulose obtained in the step 1 with 1-butyl-3 methylimidazole chloride BmimCl ionic liquid, cooling to room temperature after the nano-cellulose is completely dissolved in a constant-temperature water bath, and centrifuging in a centrifuge to wash away redundant ionic liquid;
step 3, modification of nanocellulose: uniformly mixing the nano-cellulose solution obtained in the step (2) with methyl trimethoxy silane (MTMS) in a magnetic stirrer, and carrying out surface modification on the nano-cellulose to obtain a modified nano-cellulose solution;
step 4, gelation: taking (N, N-methylene acrylamide) MBA as a cross-linking agent, blending the modified nano-cellulose solution obtained in the step (3) with the N, N-methylene acrylamide MBA cross-linking agent, ultrasonically stirring in an ultrasonic cleaning instrument until the solution is fully mixed, and standing at room temperature for hydrogel forming;
and 5, replacing and drying the aerogel: and after the gel sample is chemically cross-linked and molded, replacing the solution in the hydrogel by using deionized water, ethanol and tert-butyl alcohol solution, and freeze-drying to obtain the nano-cellulose hydrophobic aerogel.
Preferably, in the step 1, the benzene and alcohol pretreatment time is 6h, the NaOH concentration is 10wt%, the reaction temperature is 80 ℃ and the reaction time is 2h, and NaClO is added 2 The concentration is 7.5wt%, the reaction temperature is 75 ℃ and the reaction time is 3h 2 SO 4 The concentration is 45%, the reaction temperature is 45 ℃ and the reaction time is 120mins.
Preferably, in the step 2, the water bath temperature is 80 ℃, the time is 3h, the rotation speed of the centrifugal machine is 6000r/min, and the centrifugation times are 3-4.
Preferably, in the step 3, MTMS with the same weight as that of the nano-cellulose is added, and the rotating speed of the magnetic stirrer is set to be 600r/min for 2h.
Preferably, in the step 4, MBA with the same weight as the mushroom dreg nanocellulose is added, the ultrasonic treatment time is 20mins, and the standing time is 12h.
Preferably, in the step 5, the hydrogel solution is replaced for 2 times, the replacement time is 6 hours each time, freeze drying is adopted, the temperature of cold hydrazine is-55 to 60 ℃, the vacuum degree is 1 to 4Pa, and the freeze drying time is 48 hours.
The invention has the beneficial effects that:
the method for preparing the hydrophobic aerogel by using the agaric fungus residues comprises the steps of taking the waste agaric fungus residues as raw materials, effectively removing residual attachments on the surfaces of the waste agaric fungus residues through benzene and alcohol pretreatment, preparing a NaOH solution with the concentration of 10wt%, performing alkali treatment at 80 ℃ for 2 hours to remove hemicellulose, and preparing NaClO with the concentration of 7.5wt% 2 Bleaching the solution at 75 deg.C for 3h to remove lignin, extracting cellulose from the mushroom residue, and removing the residue at 45% H at 45 deg.C 2 SO 4 Performing acidolysis in the solution for 120min to obtain slender needle-shaped nano-cellulose. 1.0g,2.0g and 3.0g of nanocellulose are respectively mixed with 19g,18g and 17g of BmimCI ionic liquid, the mixture is stirred for 3 hours at the water bath temperature of 80 ℃ to be completely dissolved, and after the mixture is cooled to room temperature, the mixture is at 6000r/miAnd n, centrifuging for 3-4 times in the centrifuge to wash off the redundant ionic liquid. 1.0g,2.0g and 3.0g of MTMS are added and mixed with the same weight of nano-cellulose solution, and the mixture is stirred for 2 hours at normal temperature in a magnetic stirrer of 600r/min to obtain modified nano-cellulose suspension. Adding 1.0g,2.0g and 3.0g of MBA with the same weight as the nano-cellulose, carrying out ultrasonic treatment in an ultrasonic cleaning instrument for 20mins until the mixture is fully mixed, standing for 12h at room temperature for gel formation, respectively replacing the solution in the hydrogel with deionized water, ethanol and tert-butyl alcohol solution twice, each time for 6h, and then carrying out freeze-drying for 48h in a freeze-drying machine with the temperature of-55-60 ℃ and the vacuum degree of 1-4Pa to obtain the nano-cellulose hydrophobic aerogel.
The result obtains auricularia auriculajudae fungus sediment nano cellulose hydrophobic aerogel of high porosity, low density, can float for a long time on the surface of water, and modified aerogel keeps original loose network structure, and the surface adheres to the overlapping nano cellulose silk of crossing that is similar to network structure. The invention provides a new technical route for recycling the waste agaric residues.
Drawings
FIG. 1 is a scanning electron micrograph of a cellulose hydrophobic aerogel prepared according to example 1 of the present invention;
FIG. 2 is a graph of density and porosity of a cellulose hydrophobic aerogel prepared according to the present invention under three different conditions.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing hydrophobic aerogel by using agaric fungi residues, which comprises the following steps:
step 1, preparing nano-cellulose by an acidolysis method: the fungus dregs are first treated with benzene and alcohol organic solvent in a Soxhlet extractorPretreating with agent for 6h, alkali treating with 10wt% NaOH at 80 deg.C for 2h to remove hemicellulose, and treating with 7.5wt% NaClO 2 Washing the solution with alkali at 75 deg.C for 3 hr to remove lignin, purifying cellulose, and mixing the purified cellulose with 45wt% of H 2 SO 4 Reacting the solution at 45 ℃ for 120mins, washing with water to neutrality, and freeze-drying to obtain nano-cellulose;
step 2, dissolving nano-cellulose: mixing the nano-cellulose and the BmimCl ionic liquid in the step 1, stirring for 3 hours under the condition of 80 ℃ constant-temperature water bath until the nano-cellulose is completely dissolved, cooling to room temperature, and centrifuging for 3-4 times in a centrifuge with the rotating speed of 6000r/min to wash away the redundant ionic liquid;
step 3, modification of nanocellulose: uniformly mixing the nano-cellulose solution obtained in the step (2) with MTMS in a magnetic stirrer, and stirring for 2 hours in the magnetic stirrer at the rotating speed of 600r/min to modify the surface of the nano-cellulose;
step 4, gelation: taking (N, N-methylene acrylamide) MBA as a cross-linking agent, adding (N, N-methylene acrylamide) MBA with the same weight as that of the nano-cellulose, blending with the solution, ultrasonically stirring in an ultrasonic cleaner for 20mins until the mixture is fully mixed, and standing for 12 hours at room temperature for gel forming;
and 5, replacing and drying the aerogel: after the gel sample is chemically cross-linked and formed, replacing the solution in the hydrogel with deionized water, ethanol and tert-butyl alcohol solution twice, each time for 6 hours, and then freeze-drying for 48 hours in a freeze-drying machine with the temperature of-55-60 ℃ and the vacuum degree of 1-4Pa to obtain the nano-cellulose hydrophobic aerogel;
the waste Auricularia auricula dregs from Oak county H is selected in the experiment 2 SO 4 、NaOH、NaClO 2 The quality of BmimCl, (N, N-methylene acrylamide) MBA, MTMS and the like meets the specified requirements, the benzene and the ethanol used for pretreatment and the deionized water used for suction filtration are analytically pure, and the quality of the deionized water meets the specified technical requirements.
The components and the processing mode act as follows:
using waste mushroom dregs as raw material H 2 SO 4 Hydrolyzing and extracting the nano-cellulose. With BThe preparation method comprises the following steps of taking the mimCl ionic liquid as a nano-cellulose dispersion system, carrying out modification treatment on nano-cellulose by MTMS, taking (N, N-methylene acrylamide) MBA as a cross-linking agent, and carrying out freeze drying to obtain the nano-cellulose hydrophobic aerogel.
Example 1
Step 1, preparing nano-cellulose by an acidolysis method: the agaric fungus dregs are first pretreated with benzene and alcohol organic solvent in a Soxhlet extractor for 6h, and then are treated with 10wt% of NaOH at 80 ℃ for 2h to remove hemicellulose and 7.5wt% of NaClO 2 The solution was washed with alkali at 75 ℃ for 3H to remove lignin, purify the cellulose, and mix the purified cellulose with 45wt% H 2 SO 4 Reacting the solution at 45 ℃ for 120mins, washing with water to neutrality, and freeze-drying to obtain nano-cellulose;
and 2, dissolving the nano-cellulose: mixing 1.0g of the nano-cellulose obtained in the step 1 with 19g of BmimCl ionic liquid, stirring for 3 hours under the condition of 80 ℃ constant-temperature water bath until the nano-cellulose is completely dissolved, cooling to room temperature, and centrifuging for 3-4 times in a centrifuge with the rotating speed of 6000r/min to wash away redundant ionic liquid;
step 3, modifying the nano-cellulose: uniformly mixing the nano-cellulose solution obtained in the step (2) with 1.0g of MTMS in a magnetic stirrer, and stirring for 2 hours in the magnetic stirrer at the rotating speed of 600r/min to carry out surface modification on the nano-cellulose;
step 4, gelation: taking (N, N-methylene acrylamide) MBA as a cross-linking agent, adding 1.0g of (N, N-methylene acrylamide) MBA and a nano cellulose solution, blending, ultrasonically stirring for 20mins in an ultrasonic cleaner, fully mixing, and standing for 12 hours at room temperature for gel forming;
and 5, replacing and drying the aerogel: and after the gel sample is subjected to chemical crosslinking forming, replacing the solution in the hydrogel with deionized water, ethanol and tert-butyl alcohol solution twice each for 6 hours, and then performing freeze-drying for 48 hours in a freeze-drying machine with a cold hydrazine temperature of-55-60 ℃ and a vacuum degree of 1-4Pa to obtain the nano-cellulose hydrophobic aerogel NA1.
Example 2
Step 1, preparing nano-cellulose by an acidolysis method: auricularia auricula-judae fungi residueFirstly, pretreating for 6h by benzene and alcohol organic solvent in a Soxhlet extractor, then carrying out alkali treatment for 2h at 80 ℃ by 10wt% of NaOH to remove hemicellulose and 7.5wt% of NaClO 2 The solution was washed with alkali at 75 ℃ for 3H to remove lignin, purify the cellulose, and mix the purified cellulose with 45wt% H 2 SO 4 Reacting the solution at 45 ℃ for 120mins, washing with water to neutrality, and freeze-drying to obtain nano-cellulose;
step 2, dissolving nano-cellulose: mixing 2.0g of the nano-cellulose obtained in the step 1 with 18g of BmimCl ionic liquid, stirring for 3 hours under the condition of 80 ℃ constant-temperature water bath until the nano-cellulose is completely dissolved, cooling to room temperature, and centrifuging for 3-4 times in a centrifuge with the rotating speed of 6000r/min to wash away the redundant ionic liquid;
step 3, modification of nanocellulose: uniformly mixing the nano-cellulose solution obtained in the step (2) with 2.0g of MTMS in a magnetic stirrer, and stirring for 2 hours in the magnetic stirrer at the rotating speed of 600r/min to modify the surface of the nano-cellulose;
step 4, gelation: taking (N, N-methylene acrylamide) MBA as a cross-linking agent, adding 2.0g of (N, N-methylene acrylamide) MBA and a nano cellulose solution, blending, carrying out ultrasonic stirring in an ultrasonic cleaning instrument for 20mins until the mixture is fully mixed, and standing for 12 hours at room temperature for gel forming;
and 5, replacing and drying the aerogel: and after the gel sample is subjected to chemical crosslinking molding, replacing the solution in the hydrogel by using deionized water, ethanol and tert-butyl alcohol solution twice each for 6h, and then performing freeze-drying for 48h in a freeze-drying machine at the temperature of-55-60 ℃ and the vacuum degree of 1-4Pa to obtain the nano-cellulose hydrophobic aerogel NA2.
Example 3
Step 1, preparing nano-cellulose by an acidolysis method: the agaric fungus dregs are first pretreated with benzene and alcohol organic solvent in a Soxhlet extractor for 6h, and then are treated with 10wt% of NaOH at 80 ℃ for 2h to remove hemicellulose and 7.5wt% of NaClO 2 Washing the solution with alkali at 75 deg.C for 3 hr to remove lignin, purifying cellulose, and mixing the purified cellulose with 45wt% of H 2 SO 4 The solution reacts for 120mins at 45 ℃, is washed to be neutral by water and then is frozenDrying to obtain nano-cellulose;
and 2, dissolving the nano-cellulose: mixing 3.0g of the nano-cellulose obtained in the step 1 with 17g of BmimCl ionic liquid, stirring for 3 hours under the condition of 80 ℃ constant-temperature water bath until the nano-cellulose is completely dissolved, cooling to room temperature, and centrifuging for 3-4 times in a centrifuge with the rotating speed of 6000r/min to wash away the redundant ionic liquid;
step 3, modification of nanocellulose: uniformly mixing the nano-cellulose solution obtained in the step (2) with 3.0g of MTMS in a magnetic stirrer, and stirring for 2 hours in the magnetic stirrer at the rotating speed of 600r/min to carry out surface modification on the nano-cellulose;
step 4, gelation: taking (N, N-methylene acrylamide) MBA as a cross-linking agent, adding 3g of MBA and the nano-cellulose solution obtained in the step (3), blending, performing ultrasonic stirring in an ultrasonic cleaning instrument for 20mins until the mixture is fully mixed, and standing for 12 hours at room temperature for gel forming;
and 5, replacing and drying the aerogel: and after the gel sample is subjected to chemical crosslinking forming, replacing the solution in the hydrogel with deionized water, ethanol and tert-butyl alcohol solution twice, each replacing for 6 hours, and then freeze-drying for 48 hours in a freeze-drying machine with the temperature of-55-60 ℃ and the vacuum degree of 1-4Pa to obtain the modified nano-cellulose aerogel NA3.
Fig. 1 is a scanning electron microscope image of the hydrophobic nano-cellulose aerogel prepared in example 1 of the present invention, and it can be seen that a large number of fiber bundle filaments inside the aerogel are smooth in surface, the nano-celluloses are intertwined and randomly cross-linked, and cross-lapped nano-cellulose filaments similar to a mesh structure are attached to the surface of the aerogel. Spatially forming a network structure; according to the nano-cellulose hydrophobic aerogel prepared in the embodiment 2, the aerogel has ultra-light weight and can be stably placed on setaria viridis; according to the nano-cellulose hydrophobic aerogel prepared in the embodiment 3, after hydrophobic modification, the aerogel can be kept floating on the water surface for a long time, and a good hydrophobic effect is achieved. FIG. 2 is a graph of density and porosity of the nanocellulose hydrophobic aerogel prepared by the present invention under three different conditions, and it can be seen from FIG. 2 that the density of the hydrophobic aerogelShows a rising trend from 47.002mg/cm 3 Increased to 50.425mg/cm 3 The porosity of the aerogel has a trend opposite to the density, and gradually decreases with the increase of the content of the nanocellulose, and the porosity of the aerogel decreases from 97.044% to 96.828%.
The nano-cellulose hydrophobic aerogel prepared by the technology of the invention takes agaric fungus residues as raw materials, H 2 SO 4 Hydrolyzing to obtain nano-cellulose, taking BmimCl ionic liquid as a nano-cellulose dissolving system, performing MTMS (methyl thiazolyl tetrazolium) modified nano-cellulose, (N, N-methylene acrylamide) MBA (methyl thiazolyl tetrazolium) chemical crosslinking, and then freeze-drying to prepare the nano-cellulose with the density of 47.002mg/cm 3 The porosity is 97.044% ultra-light aerogel, intertwine between the nanometer cellulose, unordered cross-linking becomes the comparatively loose network structure of structure, and the aerogel surface forms the crisscross lapped nanometer cellulose silk of network structure, has good hydrophobic effect, can be long-time keep on the surface of water.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for preparing hydrophobic aerogel by using agaric fungi residues is characterized by comprising the following steps:
step 1, preparing nano-cellulose by an acidolysis method: the agaric residue is first pretreated with benzene and alcohol organic solvent and then treated with NaOH and NaClO 2 Alkali washing and bleaching the solution to purify the cellulose, and mixing the obtained cellulose with H 2 SO 4 Uniformly mixing the solution, fully reacting, washing to be neutral, and freeze-drying to obtain nano-cellulose;
and 2, dissolving the nano-cellulose: mixing the nano-cellulose obtained in the step 1 with 1-butyl-3 methylimidazolium chloride BmimCl ionic liquid, cooling to room temperature after the nano-cellulose is completely dissolved in a constant-temperature water bath, and centrifuging in a centrifuge to wash away redundant ionic liquid;
step 3, modification of nanocellulose: uniformly mixing the nano-cellulose solution obtained in the step (2) with methyl trimethoxy silane (MTMS) in a magnetic stirrer, and carrying out surface modification on the nano-cellulose to obtain a modified nano-cellulose solution;
step 4, gelation: taking N, N-methylene acrylamide (MBA) as a cross-linking agent, blending the modified nano-cellulose solution obtained in the step (3) with the N, N-methylene acrylamide (MBA) cross-linking agent, ultrasonically stirring in an ultrasonic cleaning instrument until the solution is fully mixed, and standing at room temperature for hydrogel forming;
and 5, replacing and drying the aerogel: and after the gel sample is subjected to chemical crosslinking molding, replacing the solution in the hydrogel by using deionized water, ethanol and tert-butyl alcohol solution, and freeze-drying to obtain the nano-cellulose hydrophobic aerogel.
2. The method for preparing hydrophobic aerogel with agaric fungi residues as claimed in claim 1, wherein in step 1, the pretreatment time of benzene and alcohol is 6h, the concentration of sodium hydroxide NaOH is 10wt%, the reaction temperature is 80 ℃ and the reaction time is 2h 2 The concentration is 7.5 weight percent, the reaction temperature is 75 ℃, the reaction time is 3h 2 SO 4 The concentration is 45%, the reaction temperature is 45 ℃ and the reaction time is 120mins.
3. The method for preparing hydrophobic aerogel from agaric fungi residues as claimed in claim 1, wherein in the step 2, the water bath temperature is 80 ℃, the time is 3h, the rotation speed of the centrifuge is 6000r/min, and the centrifugation times are 3-4.
4. The method for preparing hydrophobic aerogel by using agaric fungi residues as claimed in claim 1, wherein in the step 3, methyltrimethoxysilane (MTMS) with the same weight as the nanocellulose is added, and the rotating speed of the magnetic stirrer is set to be 600r/min for 2h.
5. The method for preparing hydrophobic aerogel by using agaric fungi residues as claimed in claim 1, wherein in the step 4, N-methylene acrylamide (MBA) with the same weight as the fungi residue nano-cellulose is added, the ultrasonic treatment time is 20mins, and the standing time is 12h.
6. The method for preparing hydrophobic aerogel from agaric fungi residues according to claim 1, wherein in the step 5, the hydrogel solution is replaced for 2 times, the replacement time is 6 hours each time, freeze drying is adopted, the temperature of cold hydrazine is-55-60 ℃, the vacuum degree is 1-4Pa, and the freeze drying time is 48 hours.
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| CN113429617A (en) * | 2021-06-24 | 2021-09-24 | 东华大学 | Kapok nano-cellulose aerogel and preparation method and application thereof |
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