CN113416343A - Waste cellulose acetate fiber-based regenerated cellulose aerogel and preparation method thereof - Google Patents
Waste cellulose acetate fiber-based regenerated cellulose aerogel and preparation method thereof Download PDFInfo
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- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 112
- 239000004964 aerogel Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 title abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 93
- 239000011259 mixed solution Substances 0.000 claims abstract description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007710 freezing Methods 0.000 claims abstract description 8
- 230000008014 freezing Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 7
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical Kinetics & Catalysis (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
The invention discloses a waste cellulose acetate fiber-based regenerated cellulose aerogel and a preparation method thereof, belonging to the technical field of composite materials. Dissolving a cigarette filter tip into the obtained sodium hydroxide/urea aqueous solution to obtain a solution system; freezing the obtained solution system, then unfreezing, and continuously adding ethanol to precipitate regenerated cellulose after unfreezing to obtain a mixed solution containing the regenerated cellulose; centrifugally washing the obtained mixed solution containing the regenerated cellulose, and drying to obtain regenerated cellulose; uniformly dispersing zinc nitrate and 2-methylimidazole in methanol to obtain a mixed solution; dispersing the obtained regenerated cellulose in the obtained mixed solution to obtain a reaction system, firstly generating the obtained reaction system in situ, loading MOF materials, and then freeze-drying to obtain the waste cellulose acetate based regenerated cellulose aerogel. The invention solves the problem that the waste cigarette filter tip can not be efficiently reused, and prepares the waste cellulose acetate fiber-based regenerated cellulose aerogel with low density, high specific surface area and high porosity.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a waste cellulose acetate based regenerated cellulose aerogel and a preparation method thereof.
Background
The cellulose aerogel has the advantages of high porosity, high specific surface area, low density, good biodegradability and the like, and has certain application prospects in the fields of mechanics, electrochemistry, thermodynamics and the like. Cellulose aerogels can be largely classified into natural cellulose aerogels, cellulose derivative aerogels, and regenerated cellulose aerogels according to the source. And the composite aerogel with the required performance can be prepared by modification, loading and other modes.
With the rapid development of human industrialization, non-renewable resources are gradually exhausted, and environmental pollution and energy crisis become two major problems facing at present. Firstly, the problem of environmental pollution is solved, environmental pollution caused by industrial development and great pressure on the environment caused by a large amount of domestic garbage, wastes and the like. Secondly, the utilization of natural sources, biodegradable and renewable biomass resources has received more and more attention. At present, related research reports can convert some waste resources into usable resources, and the waste resources can be applied to various fields, and have certain significance for two major problems of environment and resources. In daily life, the discarded cigarette filter tip is visible everywhere, causing pollution to the environment to a certain extent. Currently, cigarette filters are made from cellulose acetate, which is one of the cellulose derivatives. Cellulose acetate is dissolved in part of organic solvents such as acetic acid, acetone and the like, so that the process for directly preparing the cellulose acetate aerogel is complex, and the wide preparation and application of the cellulose acetate aerogel are limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a waste cellulose acetate fiber-based regenerated cellulose aerogel and a preparation method thereof, and solve the problem that the waste cigarette filters cannot be efficiently recycled.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of waste cellulose acetate fiber-based regenerated cellulose aerogel, which comprises the steps of preparing a sodium hydroxide/urea aqueous solution by using sodium hydroxide, urea and water, and dissolving a cigarette filter tip into the obtained sodium hydroxide/urea aqueous solution to obtain a solution system; freezing the obtained solution system, then unfreezing, and continuously adding ethanol to precipitate regenerated cellulose after unfreezing to obtain a mixed solution containing the regenerated cellulose; centrifugally washing the obtained mixed solution containing the regenerated cellulose, and drying to obtain regenerated cellulose; uniformly dispersing zinc nitrate and 2-methylimidazole in methanol to obtain a mixed solution; dispersing the obtained regenerated cellulose in the obtained mixed solution to obtain a reaction system, firstly generating the obtained reaction system in situ, loading MOF materials, and then freeze-drying to obtain the waste cellulose acetate based regenerated cellulose aerogel.
Preferably, the ratio of sodium hydroxide, urea and water is 7 wt%: 12 wt%: 81 wt% to prepare a sodium hydroxide/urea aqueous solution, and standing at the temperature of between 15 ℃ below zero and 18 ℃ below zero for 20 to 60min to obtain the sodium hydroxide/urea aqueous solution.
Preferably, the material ratio of the cigarette filter tip to the ethanol is 1-5 g: 50-200 mL.
Preferably, the obtained solution system is frozen and then thawed, and the specific operation comprises the following steps: firstly, freezing for 12-24h at the temperature of-15 to-18 ℃, and then unfreezing at normal temperature.
Preferably, the centrifuge operating parameters of the resulting mixed liquor include: the rotation speed of the centrifugation is 8000-10000r/min, and the time is 5-10 min.
Preferably, the drying condition of the obtained mixed solution containing the regenerated cellulose is 60-80 ℃.
Preferably, the feeding ratio of the zinc nitrate, the 2-methylimidazole and the methanol is 1-4 mmol: 4-16 mmol: 25 mL.
Preferably, the specific operations of generating and loading MOF material in situ are: standing for 12-24 h; the freeze drying time is 24-36 h.
The invention discloses a waste cellulose acetate fiber-based regenerated cellulose aerogel prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of waste cellulose acetate-based regenerated cellulose aerogel, which adopts low-temperature sodium hydroxide/urea as a cellulose acetate dissolution system, so that the waste cigarette filter material cellulose acetate is firstly deacetylated in an alkaline environment, and large solvent molecules are formed by the sodium hydroxide and the urea at a low temperature so that a cellulose macromolecular chain is destroyed, thereby realizing dissolution. Therefore, the technical limitation that cellulose derivatives such as cellulose acetate and the like are only dissolved in organic solvents such as acetone and the like in the prior art can be effectively avoided, the dissolving system provided by the invention is green and environment-friendly, and the introduction of the organic solvents is avoided. Meanwhile, the controlled preparation of the composite aerogel can be realized in one step by introducing an in-situ growth MOF material ZIF-8. Therefore, the preparation method has the advantages of being green, environment-friendly and controllable, overcomes the technical obstacle that acetate fibers are difficult to degrade, and further solves the problem that the waste cigarette filters cannot be efficiently reused.
The invention also discloses the waste cellulose acetate fiber-based regenerated cellulose aerogel prepared by the preparation method. In the waste cellulose acetate fiber-based regenerated cellulose aerogel, the specific surface area and the pore structure of the material can be greatly improved by introducing an MOF material ZIF-8. In addition, relevant tests show that the obtained waste cellulose acetate fiber-based regenerated cellulose aerogel has the performance advantages of low density, high specific surface area and high porosity based on the modification of the preparation method on the basis of the waste cigarette filter material, so that the waste cellulose acetate fiber-based regenerated cellulose aerogel has good adsorption capacity on organic dye, can be further applied to the field of wastewater treatment, realizes the efficient recycling of the waste cigarette filters, and achieves higher practical application value.
Drawings
FIG. 1 is a scanning electron microscope image of a waste cellulose acetate-based regenerated cellulose aerogel prepared in example 1;
FIG. 2 is a scanning electron micrograph of a waste cellulose acetate-based regenerated cellulose aerogel prepared in example 3;
fig. 3 is a scanning electron microscope image of the waste cellulose acetate-based regenerated cellulose aerogel prepared in example 5.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the 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.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention relates to a waste cellulose acetate fiber-based regenerated cellulose aerogel, which is prepared by directly dissolving and regenerating a recovered cigarette filter tip to obtain waste cellulose acetate fiber-based regenerated cellulose, loading an MOF material on the surface of the recovered cigarette filter tip through in-situ growth and combining a freeze drying technology.
The preparation method of the waste cellulose acetate based regenerated cellulose aerogel is implemented according to the following steps:
step 1, according to 7 wt%: 12 wt%: preparing 50-250mL of sodium hydroxide/urea aqueous solution by 81 wt% (sodium hydroxide: urea: water), and placing the prepared sodium hydroxide/urea aqueous solution in a refrigerator at (-15-18 ℃) for 20-60 min.
And 2, dissolving the recovered 1-5 g of cigarette filter tip in the prepared sodium hydroxide/urea aqueous solution to obtain a solution system, and freezing at the temperature of-15 to-18 ℃ for 12-24 hours.
And 3, unfreezing the frozen solution system in the step 2 at normal temperature, adding 50-200mL of ethanol, stirring vigorously, standing for 24h, and separating out regenerated cellulose to obtain a mixed solution containing the regenerated cellulose.
And 4, centrifugally washing the mixed solution prepared in the step 3 for 6-12 times at the rotating speed of 8000-10000r/min for 5-10 min. Then drying at 60-80 ℃ to obtain the regenerated cellulose.
And step 5, respectively dissolving 1-4mmol of zinc nitrate and 4-16mmol of 2-methylimidazole in 25mL of methanol solution, and mixing and stirring the two solutions for 10-20min to obtain a mixed solution.
And 6, dispersing the regenerated cellulose prepared in the step 4 in the mixed solution prepared in the step 5, standing for 12-24h at normal temperature to realize in-situ generation of the MOF, loading the MOF on the surface of the regenerated cellulose, and drying for 24-36h in a freeze dryer to prepare the waste cellulose acetate based regenerated cellulose aerogel.
Specifically, in the embodiment of the invention, the temperature of the refrigerator and the freezing treatment is-15 to-18 ℃.
Specifically, in the specific embodiment of the invention, the normal temperature environment is 10-35 ℃.
The invention can directly recycle the cigarette filter tip, has important significance for recycling the waste cigarette end, and greatly promotes the adsorption catalysis effect by compounding with the MOF material, so that the waste cellulose acetate fiber-based regenerated cellulose aerogel prepared by the invention can be used as an adsorption catalyst.
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures:
example 1
3.5g of sodium hydroxide and 6g of urea were dissolved in 40.5g of deionized water and then placed in a refrigerator for 20 min. The recovered 2g of cigarette filter was dissolved in the prepared sodium hydroxide/urea aqueous solution and then frozen for 12 hours. And then unfreezing the frozen solution system at normal temperature, adding 50mL of ethanol, stirring vigorously to precipitate regenerated cellulose, and standing for 24h to obtain a mixed solution containing the regenerated cellulose. Then the mixed solution containing regenerated cellulose is washed for 6 times by centrifugation, the rotating speed is 8000r/min, and each time is 5 min. Then drying at 60 ℃ to obtain the regenerated cellulose. 1mmol of zinc nitrate and 4mmol of 2-methylimidazole are respectively dissolved in 25mL of methanol solution, and then the two solutions are mixed and stirred for 10min to obtain a mixed solution. And dispersing the prepared regenerated cellulose in the mixed solution, standing for 12h at normal temperature, realizing in-situ generation of MOF, and loading MOF on the surface of the regenerated cellulose. And then drying the waste cellulose acetate fiber-based regenerated cellulose aerogel in a freeze dryer for 24 hours to prepare the waste cellulose acetate fiber-based regenerated cellulose aerogel.
The scanning electron microscope image of the waste cellulose acetate based regenerated cellulose aerogel prepared in the embodiment is shown in fig. 1, the surface of the waste cellulose acetate based regenerated cellulose aerogel can be seen to have an excellent porous structure, and the specific surface area of the waste cellulose acetate based regenerated cellulose aerogel measured by a Kangta specific surface area measuring instrument is 110m2The specific surface area is greatly increased compared to comparative example 1. The specific surface area of the composite material can be effectively improved by loading the ZIF-8. The density was calculated to be about 0.036g/cm by dividing the mass by the volume3。
Example 2
3.5g of sodium hydroxide and 6g of urea were dissolved in 40.5g of deionized water and then placed in a refrigerator for 20 min. The recovered 1g of cigarette filter was dissolved in the prepared sodium hydroxide/urea aqueous solution and then frozen for 12 hours. And then unfreezing the frozen solution system at normal temperature, adding 50mL of ethanol, stirring vigorously to precipitate regenerated cellulose, and standing for 24h to obtain a mixed solution containing the regenerated cellulose. Then the mixed solution containing regenerated cellulose is washed 8 times by centrifugation, the rotating speed is 10000r/min, and each time is 5 min. Then drying at 80 ℃ to obtain the regenerated cellulose. 1mmol of zinc nitrate and 4mmol of 2-methylimidazole are respectively dissolved in 25mL of methanol solution, and then the two solutions are mixed and stirred for 10min to obtain a mixed solution. And dispersing the prepared regenerated cellulose in the mixed solution, standing for 24h at normal temperature, realizing in-situ generation of MOF, and loading MOF on the surface of the regenerated cellulose. And then drying the waste cellulose acetate fiber-based regenerated cellulose aerogel in a freeze dryer for 28 hours to prepare the waste cellulose acetate fiber-based regenerated cellulose aerogel.
The waste cellulose acetate fiber-based regenerated cellulose aerogel prepared in the embodiment has a specific surface area of about 126m measured by Kangta specific surface area tester2(iv)/g, calculated by dividing the mass by the volume, has a density of about 0.032g/cm3。
Example 3
14g of sodium hydroxide and 24g of urea were dissolved in 162g of deionized water and then placed in a refrigerator for 20 min. The recovered 5g of cigarette filter was dissolved in the prepared aqueous solution of sodium hydroxide/urea and then frozen for 12 hours. And then unfreezing the frozen solution system at normal temperature, adding 150mL of ethanol, stirring vigorously to precipitate regenerated cellulose, and standing for 24h to obtain a mixed solution containing the regenerated cellulose. Then the mixed solution containing regenerated cellulose is washed 10 times by centrifugation, the rotating speed is 10000r/min, and each time is 5 min. Then drying at 65 ℃ to obtain regenerated cellulose. 4mmol of zinc nitrate and 16mmol of 2-methylimidazole are respectively dissolved in 25mL of methanol solution, and then the two solutions are mixed and stirred for 20min to obtain a mixed solution. And dispersing the prepared regenerated cellulose in the mixed solution, standing for 18h at normal temperature, realizing in-situ generation of MOF, and loading MOF on the surface of the regenerated cellulose. And then drying the waste cellulose acetate fiber-based regenerated cellulose aerogel in a freeze dryer for 24 hours to prepare the waste cellulose acetate fiber-based regenerated cellulose aerogel.
The scanning electron microscope image of the waste cellulose acetate based regenerated cellulose aerogel prepared by the embodiment is shown in fig. 2, the excellent pore structure can be clearly seen, the ZIF-8 crystals are dispersed in the surface and internal pore structures, and the specific surface area of the waste cellulose acetate based regenerated cellulose aerogel measured by a kangta specific surface area tester is up to 1020m2The density of the ZIF-8 successfully generated and greatly improved composite aerogel is calculated to be about 0.05g/cm through dividing the mass by the volume3。
Example 4
7g of sodium hydroxide and 12g of urea were dissolved in 81g of deionized water and then placed in a refrigerator for 40 min. The recovered 4g of cigarette filter was dissolved in the prepared aqueous sodium hydroxide/urea solution and then frozen for 18 h. And then unfreezing the frozen solution system at normal temperature, adding 100mL of ethanol, stirring vigorously to precipitate regenerated cellulose, and standing for 24h to obtain a mixed solution containing the regenerated cellulose. The mixed solution containing regenerated cellulose is washed by centrifugation for 12 times, the rotating speed is 9000r/min, and each time is 8 min. Then drying at 70 ℃ to obtain regenerated cellulose. 2mmol of zinc nitrate and 8mmol of 2-methylimidazole are respectively dissolved in 25mL of methanol solution, and then the two solutions are mixed and stirred for 15min to obtain a mixed solution. And dispersing the prepared regenerated cellulose in the mixed solution, standing for 12h at normal temperature to realize in-situ generation of MOF, loading MOF on the surface of the regenerated cellulose, and drying for 30h in a freeze dryer to prepare the waste cellulose acetate based regenerated cellulose aerogel.
The waste cellulose acetate fiber-based regenerated cellulose aerogel prepared by the embodiment has the specific surface area as high as 800m measured by a Kangta specific surface area tester2(iv)/g, calculated by dividing the mass by the volume, has a density of about 0.042g/cm3。
Example 5
17.5g of sodium hydroxide and 30g of urea were dissolved in 202g of deionized water and then placed in a refrigerator for 60 min. The recovered 5g of cigarette filter was dissolved in the prepared aqueous sodium hydroxide/urea solution and then frozen for 24 h. And then unfreezing the frozen solution system at normal temperature, adding 200mL of ethanol, stirring vigorously to precipitate regenerated cellulose, and standing for 24h to obtain a mixed solution containing the regenerated cellulose. The mixed solution containing regenerated cellulose is washed by centrifugation for 12 times, the rotating speed is 8000r/min, and each time lasts for 10 min. Then drying at 80 ℃ to obtain the regenerated cellulose. 4mmol of zinc nitrate and 16mmol of 2-methylimidazole are respectively dissolved in 25mL of methanol solution, and then the two solutions are mixed and stirred for 20min to obtain a mixed solution. And dispersing the prepared regenerated cellulose in the mixed solution, standing for 24h at normal temperature, realizing in-situ generation of MOF, and loading MOF on the surface of the regenerated cellulose. And drying for 36 hours in a freeze dryer to obtain the waste cellulose acetate base regenerated cellulose aerogel.
The scanning electron microscope image of the waste cellulose acetate based regenerated cellulose aerogel prepared in this example is shown in fig. 3, and comparative example 1 can clearly see that a large amount of ZIF-8 crystals are dispersed on the surface. And the specific surface area of the material is up to 914m measured by a kangta specific surface area testing instrument2The successful ZIF-8 content was high, with a density of about 0.064g/cm calculated by dividing mass by volume3。
Specifically, in the above embodiment of the present invention, the temperature of the refrigerator and the freezing treatment is-15 to-18 ℃.
Specifically, in the above embodiment of the present invention, the normal temperature environment is 10 to 35 ℃.
Comparative example 1
3.5g of sodium hydroxide and 6g of urea were dissolved in 40.5g of deionized water and then placed in a refrigerator for 20 min. The recovered 2g of cigarette filter was dissolved in the prepared sodium hydroxide/urea aqueous solution and then frozen for 12 hours. And then unfreezing the frozen solution system at normal temperature, adding 50mL of ethanol, stirring vigorously to precipitate regenerated cellulose, and standing for 24h to obtain a mixed solution containing the regenerated cellulose. Then the mixed solution containing regenerated cellulose is washed for 6 times by centrifugation, the rotating speed is 8000r/min, and each time is 5 min. And then drying at 60 ℃ to obtain regenerated cellulose, dispersing in water, and drying in a freeze dryer for 24 hours to obtain the regenerated cellulose aerogel.
The regenerated cellulose aerogel prepared in the embodiment has a specific surface area of 40m measured by Kangta specific surface area tester2(ii) in terms of/g. The density was calculated to be about 0.028g/cm by dividing the mass by the volume3。
In conclusion, the invention provides the waste cellulose acetate based regenerated cellulose aerogel and the preparation method thereof, and provides a new way for recycling the cigarette filter tip. The recycled cigarette filter tip is directly regenerated by dissolution, and MOF materials are loaded on the surface of the recycled cigarette filter tip through in-situ growth, so that the waste cellulose acetate fiber-based regenerated cellulose aerogel with low density, high specific surface area and high porosity is obtained. The obtained waste cellulose acetate fiber-based regenerated cellulose aerogel has a high specific surface area and a good porous structure, so that the waste cellulose acetate fiber-based regenerated cellulose aerogel has good potential for adsorbing organic dyes and can be applied to the field of wastewater treatment.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of waste cellulose acetate based regenerated cellulose aerogel is characterized in that sodium hydroxide/urea aqueous solution is prepared by using sodium hydroxide, urea and water, and a cigarette filter tip is dissolved in the obtained sodium hydroxide/urea aqueous solution to obtain a solution system; freezing the obtained solution system, then unfreezing, and continuously adding ethanol to precipitate regenerated cellulose after unfreezing to obtain a mixed solution containing the regenerated cellulose; centrifugally washing the obtained mixed solution containing the regenerated cellulose, and drying to obtain regenerated cellulose;
uniformly dispersing zinc nitrate and 2-methylimidazole in methanol to obtain a mixed solution; dispersing the obtained regenerated cellulose in the obtained mixed solution to obtain a reaction system, firstly generating the obtained reaction system in situ, loading MOF materials, and then freeze-drying to obtain the waste cellulose acetate based regenerated cellulose aerogel.
2. The method for preparing the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, wherein the feeding ratio of sodium hydroxide, urea and water is 7 wt%: 12 wt%: 81 wt% to prepare a sodium hydroxide/urea aqueous solution, and standing at the temperature of between 15 ℃ below zero and 18 ℃ below zero for 20 to 60min to obtain the sodium hydroxide/urea aqueous solution.
3. The preparation method of the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, wherein the material ratio of the cigarette filter tip to the ethanol is 1-5 g: 50-200 mL.
4. The method for preparing the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, wherein the obtained solution system is frozen and then thawed, and the specific operations comprise: firstly, freezing for 12-24h at the temperature of-15 to-18 ℃, and then unfreezing at normal temperature.
5. The method for preparing the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, wherein the centrifugal operation parameters of the obtained mixed solution comprise: the rotation speed of the centrifugation is 8000-10000r/min, and the time is 5-10 min.
6. The method for preparing the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, wherein the drying condition of the obtained mixed solution containing regenerated cellulose is 60-80 ℃.
7. The method for preparing the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, wherein the feeding ratio of zinc nitrate, 2-methylimidazole and methanol is 1-4 mmol: 4-16 mmol: 25 mL.
8. The method for preparing the waste cellulose acetate based regenerated cellulose aerogel according to claim 1, characterized in that the specific operations of in-situ generation and loading of MOF material are as follows: standing for 12-24 h;
the freeze drying time is 24-36 h.
9. A waste cellulose acetate based regenerated cellulose aerogel prepared by the preparation method of any one of claims 1 to 8.
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