CN108484962B - Method for preparing cellulose composite aerogel from waste paper - Google Patents

Method for preparing cellulose composite aerogel from waste paper Download PDF

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CN108484962B
CN108484962B CN201810214339.XA CN201810214339A CN108484962B CN 108484962 B CN108484962 B CN 108484962B CN 201810214339 A CN201810214339 A CN 201810214339A CN 108484962 B CN108484962 B CN 108484962B
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waste paper
cellulose
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composite aerogel
drying
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CN108484962A (en
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任芳
李贞�
任鹏刚
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Blue Smoke New Material Technology Co ltd
Wu Yuxiao
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Xian University of Technology
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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • 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
    • C08J2201/048—Elimination of a frozen liquid phase
    • C08J2201/0482—Elimination of a frozen liquid phase the liquid phase being organic
    • 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
    • C08J2201/048—Elimination of a frozen liquid phase
    • C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret

Abstract

The invention discloses a method for preparing cellulose composite aerogel from waste paper, which comprises the steps of firstly processing the waste paper into waste paper fiber powder, soaking the waste paper fiber powder into alkali solution, carrying out reflux reaction in an oil bath pan, filtering, ultrasonically dispersing filter residue into ethanol, and then soaking the filter residue into H2O2Filtering the solution, collecting filter residues, and drying to obtain waste paper cellulose; and then adding the waste paper cellulose into the carbon mixed solution for dissolution reaction, adding KCl, stirring, freezing and unfreezing the waste paper cellulose solution, sequentially soaking the waste paper cellulose solution in ethanol and deionized water, and finally performing freeze drying to obtain the waste paper cellulose composite aerogel. The method takes the waste paper as a raw material, prepares the waste paper cellulose composite aerogel by adding the graphene or the graphene oxide, has the characteristics of light weight, large specific surface area, high porosity, good mechanical property and the like, and is simple in process, low in production cost and suitable for batch production.

Description

Method for preparing cellulose composite aerogel from waste paper
Technical Field
The invention belongs to the technical field of preparation of polymer composite materials, and particularly relates to a method for preparing cellulose composite aerogel from waste paper.
Background
In recent years, dye waste water generated by printing factories, textile factories and the like is increasing, and most dyes contain aromatic ring structures, have certain toxicity and are difficult to degrade, seriously damage the environment and harm human health. The cellulose composite aerogel which is newly appeared on the basis of gel materials at present is a composite aerogel which is light in weight, large in specific surface area and high in porosity and is obtained by taking cellulose as a base material and compounding nano fillers, can form intermolecular force with dye molecules to achieve the purposes of adsorption and purification, has potential development in the fields of oil stain leakage, wastewater purification and the like, and becomes a hot spot and a key point of domestic and foreign research. However, the cellulose composite aerogel material has high cost, limited adsorption performance and uneven dispersion of the nano filler. Therefore, the key point of improving the dye adsorption amount in the wastewater is to find a nano filler with low cost, high adsorption performance and good dispersibility.
The annual average yield of waste paper in China is huge, the waste paper is taken as one of cellulose sources, has the characteristics of wide sources, low price, easy obtaining and the like, the waste paper contains about 50% of cellulose, and the waste paper cellulose extracted by simple pretreatment is taken as a matrix material of the composite aerogel, so that the cost is reduced while the original adsorption performance is maintained, the composite aerogel matrix material is green and environment-friendly, and is an ideal composite aerogel matrix material. However, the single waste paper cellulose aerogel is simple in structure, unstable in performance and low in removal rate of the dye, and other adsorption fillers are required to be compounded to form the composite aerogel, so that the structural characteristics and the comprehensive performance are improved.
Disclosure of Invention
The invention aims to provide a method for preparing cellulose composite aerogel from waste paper, which improves the adsorption performance of the cellulose composite aerogel on dye molecules.
The invention adopts the technical scheme that a method for preparing cellulose composite aerogel from waste paper comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and sieving the waste paper to obtain waste paper fiber powder;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 1-2 h, performing reflux reaction in an oil bath kettle at the temperature of 80-90 ℃ for 4-5 h, and filtering the reaction solution to be neutral by using a 250-mesh nylon gauze filter screen cloth after the reflux reaction is finished to obtain solid filter residue a;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain the productWaste paper cellulose;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing the carbon-series substance in the cellulose mixed solution, and then freezing the carbon-series substance to obtain a carbon-series mixed solution;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring at room temperature for 10-30 min to obtain a waste paper cellulose solution;
and 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at the temperature of between 25 ℃ below zero and 20 ℃ below zero for 24 hours, then unfreezing the waste paper cellulose solution at the temperature of between 20 ℃ and 25 ℃ for 3 hours to 4 hours to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 24 hours to 48 hours, then soaking the waste paper cellulose solution in deionized water for 24 hours to 48 hours to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel.
The present invention is also characterized in that,
in the step 1.1, the drying temperature is 40-60 ℃, and the drying time is 12-24 h; the screen mesh of 300-400 meshes is adopted during sieving.
In the step 1.2, the alkali solution is NaOH solution with the mass fraction of 3-5% or KOH solution with the mass fraction of 3-5%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 20 to 35.
In the step 1.3, the ultrasonic dispersion time is 1-2 h, and the mass ratio of the solid filter residue a to the ethanol is 1: 5 to 30.
In the step 1.4, the soaking time is 3-4 h, and the soaking temperature is 20-25 ℃; the drying temperature is 40-60 ℃, and the drying time is 12-24 h.
In the step 2.1, the time of ultrasonic dispersion is 1-2 h; the freezing temperature is-12 ℃ to-15 ℃, and the freezing time is 6h to 12 h.
In step 2.1, the mass ratio of the carbon-based substance to the cellulose mixed solution is 1: 20-100 parts of; the carbon-based substance is graphene or graphene oxide; the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water.
In the step 2.2, the mass ratio of the waste paper cellulose to the carbon mixed solution to the solid cross-linking agent KCl is 0.3-0.5: 1: 0.15 to 0.2; the dissolution reaction time is 0.5h to 1h, the dissolution reaction temperature is-15 ℃ to-10 ℃,
in the step 2.3, the freeze drying temperature is 55 ℃, and the freeze drying time is 48-72 h.
The method has the advantages that the cellulose composite aerogel is prepared by taking the waste paper as the raw material, has the characteristics of environmental protection, cyclic utilization, low economic benefit and the like, and is simple in process, low in production cost and suitable for batch production.
Drawings
FIG. 1 is an SEM image of a waste paper cellulose/GO composite aerogel in a process for preparing cellulose composite aerogel from waste paper in accordance with the present invention;
FIG. 2 is an SEM image of a waste paper cellulose/GNS composite aerogel in a process for preparing a cellulose composite aerogel from waste paper according to the present invention;
FIG. 3 is a graph of absorbance of methylene blue and Congo red for a waste paper cellulose/GO composite aerogel and pure waste paper fiber aerogel without added carbon in a process for making cellulose composite aerogel from waste paper according to the present invention;
FIG. 4 is a graph showing the absorbance curves of waste paper cellulose/GNS composite aerogel and pure waste paper fiber aerogel without added carbon for methylene blue and Congo red in a method of preparing cellulose composite aerogel from waste paper according to the present invention;
FIG. 5 is a graph showing the adsorption amounts of waste paper cellulose/GO, waste paper cellulose/GNS composite aerogel and pure waste paper fiber aerogel without carbon series added in the method for preparing cellulose composite aerogel from waste paper according to the present invention to methylene blue and Congo red.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a method for preparing cellulose composite aerogel from waste paper, which comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and sieving the waste paper to obtain waste paper fiber powder;
wherein the drying temperature is 40-60 ℃, the drying time is 12-24 h, and a 300-400 mesh screen is adopted during sieving;
the waste paper is waste books and periodicals, waste newspaper or waste paper boxes;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 1-2 h, performing reflux reaction in an oil bath kettle at the temperature of 80-90 ℃ for 4-5 h, and filtering the reaction solution to be neutral by using a 250-mesh nylon gauze filter screen cloth after the reflux reaction is finished to obtain solid filter residue a;
wherein the alkali solution is NaOH solution with the mass fraction of 3-5% or KOH solution with the mass fraction of 3-5%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 20-35;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
wherein the ultrasonic dispersion time is 1-2 h, and the mass ratio of the solid filter residue a to the ethanol is 1: 5-30;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
wherein the soaking time is 3-4 h, and the soaking temperature is 20-25 ℃;
the drying temperature is 40-60 ℃, and the drying time is 12-24 h;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing the carbon-series substance in the cellulose mixed solution, and then freezing the carbon-series substance to obtain a carbon-series mixed solution;
wherein the time of ultrasonic dispersion is 1-2 h;
the mass ratio of the carbon-series substance to the cellulose mixed solution is 1: 20-100 parts of;
the carbon-based substance is graphene or graphene oxide;
the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
the freezing temperature is-12 ℃ to-15 ℃, and the freezing time is 6h to 12 h;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring at room temperature for 10-30 min to obtain a waste paper cellulose solution;
wherein the mass ratio of the waste paper cellulose to the carbon-based mixed solution to the solid cross-linking agent KCl is 0.3-0.5: 1: 0.15 to 0.2;
the dissolution reaction time is 0.5h to 1h, and the dissolution reaction temperature is-15 ℃ to-10 ℃;
step 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at-25 ℃ to-20 ℃ for 24 hours, then unfreezing at 20 ℃ to 25 ℃ for 3 hours to 4 hours to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 24 hours to 48 hours, then soaking the waste paper cellulose solution in deionized water for 24 hours to 48 hours to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel;
wherein, during freeze drying, a freeze dryer with the model of FD-1A-50 is adopted, the freeze drying temperature is 55 ℃, and the freeze drying time is 48-72 h.
Example 1
The invention relates to a method for preparing cellulose composite aerogel from waste paper, which comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and screening the waste books and periodicals to obtain waste paper fiber powder;
wherein the drying temperature is 60 ℃, the drying time is 12h, and a 250-mesh screen is adopted during sieving;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 1h, then carrying out reflux reaction in an oil bath kettle at 80 ℃ for 4h, and after the reflux reaction is finished, filtering the reaction liquid to be neutral by using a 250-mesh nylon gauze filter screen cloth to obtain solid filter residue a;
wherein the alkali solution is a NaOH solution with the mass fraction of 4%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 20;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
wherein the ultrasonic dispersion time is 1h, and the mass ratio of the solid filter residue a to the ethanol is 1: 20;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
wherein the soaking time is 3h, and the soaking temperature is 20 ℃;
the drying temperature is 40 ℃, and the drying time is 12 h;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing graphene in a cellulose mixed solution, and then freezing the graphene to obtain a carbon-series mixed solution;
wherein the time of ultrasonic dispersion is 1 h;
the mass ratio of the graphene to the cellulose mixed solution is 1: 20;
the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring for 10min at room temperature to obtain a waste paper cellulose solution;
wherein the mass ratio of the waste paper cellulose to the carbon mixed solution to the solid cross-linking agent KCl is 0.3: 1: 0.15;
the dissolution reaction time is 0.5h, and the dissolution reaction temperature is-15 ℃;
step 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at-25 ℃ for 24 hours, then unfreezing at 20 ℃ for 3 hours to gelatinize the waste paper cellulose solution, then sequentially placing the waste paper cellulose solution into ethanol and water to be respectively soaked for 12 hours to obtain composite hydrogel, and finally performing freeze drying to obtain the waste paper cellulose composite aerogel;
wherein, during freeze drying, a freeze dryer with the model of FD-1A-50 is adopted, the freeze drying temperature is 55 ℃, and the freeze drying time is 48 h.
Example 2
The invention relates to a method for preparing cellulose composite aerogel from waste paper, which comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and sieving the waste newspaper to obtain waste paper fiber powder;
wherein the drying temperature is 40 ℃, the drying time is 12h, and a 300-mesh screen is adopted during sieving;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 1h, performing reflux reaction in an oil bath kettle at 85 ℃ for 4h, and filtering the reaction solution to be neutral by using a 250-mesh nylon gauze filter screen after the reflux reaction is finished to obtain solid filter residue a;
wherein the alkali solution is a NaOH solution with the mass fraction of 5%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 28;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
wherein the ultrasonic dispersion time is 1h, and the mass ratio of the solid filter residue a to the ethanol is 1: 20;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, and then mixing the mixed solutionFiltering to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
wherein the soaking time is 3h, and the soaking temperature is 20 ℃;
the drying temperature is 50 ℃, and the drying time is 20 h;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing graphene in a cellulose mixed solution, and then freezing the graphene to obtain a carbon-series mixed solution;
wherein the time of ultrasonic dispersion is 1 h;
the mass ratio of the graphene to the cellulose mixed solution is 1: 50;
the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
the freezing temperature is-15 ℃, and the freezing time is 12 h;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring at room temperature for 15min to obtain a waste paper cellulose solution;
wherein the mass ratio of the waste paper cellulose to the carbon mixed solution to the solid cross-linking agent KCl is 0.3: 1: 0.2;
the dissolution reaction time is 0.5h, and the dissolution reaction temperature is-15 ℃;
step 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at-20 ℃ for 24h, then unfreezing at 25 ℃ for 3h to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 24h, then soaking the waste paper cellulose solution in deionized water for 24h to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel;
wherein, during freeze drying, a freeze dryer with the model of FD-1A-50 is adopted, the freeze drying temperature is 55 ℃, and the freeze drying time is 48 h.
Example 3
The invention relates to a method for preparing cellulose composite aerogel from waste paper, which comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and sieving the waste newspaper to obtain waste paper fiber powder;
wherein the drying temperature is 50 ℃, the drying time is 12h, and a 400-mesh screen is adopted during sieving;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 1h, then carrying out reflux reaction in an oil bath kettle at 80 ℃ for 4h, and after the reflux reaction is finished, filtering the reaction liquid to be neutral by using a 250-mesh nylon gauze filter screen cloth to obtain solid filter residue a;
wherein the alkali solution is a NaOH solution with the mass fraction of 4%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 30, of a nitrogen-containing gas;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
wherein the ultrasonic dispersion time is 1h, and the mass ratio of the solid filter residue a to the ethanol is 1: 20;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
wherein the soaking time is 3h, and the soaking temperature is 20 ℃;
the drying temperature is 40 ℃, and the drying time is 12 h;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing graphene in a cellulose mixed solution, and then freezing the graphene to obtain a carbon-series mixed solution;
wherein the ultrasonic dispersion time is 1.5 h;
the mass ratio of the graphene to the cellulose mixed solution is 1: 100, respectively;
the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
the freezing temperature is-12 ℃, and the freezing time is 12 h;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring for 10min at room temperature to obtain a waste paper cellulose solution;
wherein the mass ratio of the waste paper cellulose to the carbon mixed solution to the solid cross-linking agent KCl is 0.5: 1: 0.2;
the dissolution reaction time is 1h, and the dissolution reaction temperature is-15 ℃;
step 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at-25 ℃ for 24h, then unfreezing at 20 ℃ for 3h to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 24h, then soaking the waste paper cellulose solution in deionized water for 24h to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel;
wherein, during freeze drying, a freeze dryer with the model of FD-1A-50 is adopted, the freeze drying temperature is 55 ℃, and the freeze drying time is 48 h.
Example 4
The invention relates to a method for preparing cellulose composite aerogel from waste paper, which comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and screening the waste paper boxes to obtain waste paper fiber powder;
wherein the drying temperature is 50 ℃, the drying time is 12h, and a 300-mesh screen is adopted during sieving;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 2 hours, then carrying out reflux reaction in an oil bath kettle at 85 ℃ for 4 hours, and after the reflux reaction is finished, filtering the reaction liquid to be neutral by using a 250-mesh nylon gauze filter screen cloth to obtain solid filter residue a;
wherein the alkali solution is a NaOH solution with the mass fraction of 4%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 27;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
wherein the ultrasonic dispersion time is 2h, and the mass ratio of the solid filter residue a to the ethanol is 1: 20;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
wherein the soaking time is 3h, and the soaking temperature is 25 ℃;
the drying temperature is 60 ℃, and the drying time is 24 hours;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing graphene oxide in a cellulose mixed solution, and then freezing the mixture to obtain a carbon-series mixed solution;
wherein the time of ultrasonic dispersion is 1 h;
the mass ratio of the graphene oxide to the cellulose mixed solution is 1: 20;
the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
the freezing temperature is-12 ℃, and the freezing time is 12 h;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring for 30min at room temperature to obtain a waste paper cellulose solution;
wherein the mass ratio of the waste paper cellulose to the carbon mixed solution to the solid cross-linking agent KCl is 0.3: 1: 0.15;
the dissolution reaction time is 0.5h, and the dissolution reaction temperature is-10 ℃;
step 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at-25 ℃ for 24 hours, then unfreezing at 25 ℃ for 4 hours to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 48 hours, then soaking the waste paper cellulose solution in deionized water for 48 hours to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel;
wherein, during freeze drying, a freeze dryer with the model of FD-1A-50 is adopted, the freeze drying temperature is 55 ℃, and the freeze drying time is 72 hours.
Example 5
The invention relates to a method for preparing cellulose composite aerogel from waste paper, which comprises the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and screening the waste books and periodicals to obtain waste paper fiber powder;
wherein the drying temperature is 50 ℃, the drying time is 12h, and a 300-mesh screen is adopted during sieving;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 2 hours, then carrying out reflux reaction in an oil bath kettle at 85 ℃ for 5 hours, and after the reflux reaction is finished, filtering the reaction liquid to be neutral by using a 250-mesh nylon gauze filter screen cloth to obtain solid filter residue a;
wherein the alkali solution is a KOH solution with the mass fraction of 4%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 27;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
wherein the ultrasonic dispersion time is 2h, and the mass ratio of the solid filter residue a to the ethanol is 1: 20;
step 1.4, soaking the solid filter residue b obtained in the step 1.3 in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
wherein the soaking time is 4h, and the soaking temperature is 25 ℃;
the drying temperature is 60 ℃, and the drying time is 24 hours;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing graphene oxide in a cellulose mixed solution, and then freezing the mixture to obtain a carbon-series mixed solution;
wherein the time of ultrasonic dispersion is 1 h;
the mass ratio of the graphene oxide to the cellulose mixed solution is 1: 100, respectively;
the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
the freezing temperature is-12 ℃, and the freezing time is 12 h;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring for 10min at room temperature to obtain a waste paper cellulose solution;
wherein the mass ratio of the waste paper cellulose to the carbon mixed solution to the solid cross-linking agent KCl is 0.5: 1: 0.2;
the dissolution reaction time is 1h, and the dissolution reaction temperature is-10 ℃;
step 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at-25 ℃ for 24 hours, then unfreezing at 25 ℃ for 4 hours to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 48 hours, then soaking the waste paper cellulose solution in deionized water for 48 hours to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel;
wherein, during freeze drying, a freeze dryer with the model of FD-1A-50 is adopted, the freeze drying temperature is 55 ℃, and the freeze drying time is 72 hours.
The waste paper cellulose composite aerogel with the three-dimensional network hole structure, which is prepared by the invention, has the characteristics of light weight, large specific surface area, high porosity and the like, and meanwhile, the cellulose composite aerogel has better mechanical properties and can not have serious structural collapse phenomenon in water.
According to the method, the waste paper in life is used as a raw material, and a small amount of graphene or graphene oxide is added to prepare the waste paper cellulose composite aerogel, so that the adsorption effect on the dye is greatly improved; meanwhile, the method is simple in preparation process, short in period, green and environment-friendly, low in production cost and in line with the sustainable development concept.
As shown in fig. 1 and 2, a fiber network structure and a lamellar graphene structure can be obviously observed in fig. 1, and graphene lamellar layers are uniformly dispersed and attached to an interwoven cellulose structure to form a hole structure with three-dimensional network crosslinking; in the figure 2, a layered hole structure can be obviously observed, the holes are uniform, the waste paper cellulose and the graphene oxide are obviously crosslinked, and the three-dimensional hole structure can well realize the adsorption of the dye.
The absorbance curves of the waste paper cellulose/GO composite aerogel (CGO), the waste paper cellulose/GNS composite aerogel (CGNS) and pure waste paper fiber aerogel (CA) without carbon series added to Methylene Blue (MB) and Congo Red (CR) under different wavelengths are shown in figures 3 and 4, wherein the standard concentrations of MB and CR are both 80mmol/L, the adsorption time is 12h, the mass of the adsorbent is 0.02g, the dye is 20ml, the absorption is carried out at room temperature, the supernatant of the dye solution is taken after the adsorption, and the visible spectrophotometer with the type 723 is adopted for detection.
As can be seen from fig. 3, compared with CA, the absorbance peak of the CGO composite aerogel for MB dye is significantly decreased at λ 664nm, which indicates that the adsorption effect is better and the removal rate of the dye is higher. Similarly, as can be seen from fig. 4, the absorbance value of the CGNS composite aerogel against CR is significantly decreased compared to CA at λ 498nm, which indicates that the dye concentration is decreased after adsorption, and the dye can be effectively removed. The reason is that the three-dimensional network cross-linked structure of the CA can store and adsorb a large amount of dye molecules, and a large amount of hydroxyl exists on the surface of the waste newspaper fiber, so that hydrogen bonding force exists in the dye solution, and a large amount of dye molecules are removed. And the carboxyl anion group carried by the CGO and the cation group in the MB solution form electrostatic acting force, and six-membered benzene ring of the CGNS and the azo group in the CR dye easily form pi-pi bond accumulation, so that dye molecules are adsorbed by the composite aerogel to achieve the purpose of removing the dye.
The adsorption amount of the waste paper cellulose/GO (CGO), waste paper cellulose/GNS composite aerogel (CGNS) prepared by the method disclosed by the invention and pure waste paper fiber aerogel (CA) without carbon series added to MB and CR are shown in a graph in figure 5, and as can be seen from the graph, the adsorption amounts of CA to MB and CR are about the same as 22.5mg/g, the adsorption amount of CGO to MB can reach 54.2mg/g, and the adsorption amount of CR to CR is 17.9mg/g, because carboxyl anions in CGO and anions in CR dye solution form repulsive force, so that the adsorption amount is reduced. In contrast, the adsorption amount of the CGNS on the MB is increased slightly compared with that of the CA on the MB, which shows that the CGNS only has little action force on the cation in the MB, and the adsorption amount on the CR dye can reach 48.9mg/g due to the action force of the pi-pi bond.

Claims (6)

1. A method for preparing cellulose composite aerogel from waste paper is characterized by comprising the following specific steps:
step 1, preparing waste paper cellulose, which comprises the following specific steps:
step 1.1, sequentially drying, crushing and sieving the waste paper to obtain waste paper fiber powder;
step 1.2, soaking the waste paper fiber powder obtained in the step 1.1 in an alkali solution for 1-2 h, performing reflux reaction in an oil bath kettle at the temperature of 80-90 ℃ for 4-5 h, and filtering the reaction solution to be neutral by using a 250-mesh nylon gauze filter screen cloth after the reflux reaction is finished to obtain solid filter residue a;
the alkali solution is NaOH solution with the mass fraction of 3-5% or KOH solution with the mass fraction of 3-5%; the mass ratio of the waste paper fiber powder to the alkali solution is 1: 20-35;
step 1.3, ultrasonically dispersing the solid filter residue a obtained in the step 1.2 in ethanol to obtain a dispersion liquid, and then filtering the dispersion liquid to be neutral by adopting a 250-mesh nylon gauze filter screen cloth to obtain a solid filter residue b;
step 1.4, the method of step 1.3Soaking the solid filter residue b in H with the mass fraction of 30%2O2Obtaining a mixed solution, filtering the mixed solution to be neutral by adopting a 250-mesh nylon gauze filter screen cloth, collecting filter residues, and then putting the filter residues into an oven for drying to obtain waste paper cellulose;
step 2, after the step 1, preparing the waste paper cellulose composite aerogel by using the waste paper cellulose, and specifically comprises the following steps:
step 2.1, ultrasonically dispersing the carbon-series substance in the cellulose mixed solution, and then freezing the carbon-series substance to obtain a carbon-series mixed solution;
the mass ratio of the carbon-series substance to the cellulose mixed solution is 1: 20-100 parts of; the carbon-based substance is graphene or graphene oxide; the cellulose mixed solution is prepared from the following components in percentage by mass of 7: 12: 81 NaOH, urea and water;
step 2.2, after the step 2.1, adding the waste paper cellulose in the step 1 into a carbon-series mixed solution for dissolution reaction, then adding a solid cross-linking agent KCl, and stirring at room temperature for 10-30 min to obtain a waste paper cellulose solution;
the mass ratio of the waste paper cellulose to the carbon-based mixed solution to the solid cross-linking agent KCl is 0.3-0.5: 1: 0.15 to 0.2; the dissolution reaction time is 0.5h to 1h, and the dissolution reaction temperature is-15 ℃ to-10 ℃;
and 2.3, freezing the waste paper cellulose solution obtained in the step 2.2 at the temperature of between 25 ℃ below zero and 20 ℃ below zero for 24 hours, then unfreezing the waste paper cellulose solution at the temperature of between 20 ℃ and 25 ℃ for 3 hours to 4 hours to gelatinize the waste paper cellulose solution, then soaking the waste paper cellulose solution in ethanol for 24 hours to 48 hours, then soaking the waste paper cellulose solution in deionized water for 24 hours to 48 hours to obtain composite hydrogel, and finally, freeze-drying the composite hydrogel to obtain the waste paper cellulose composite aerogel.
2. The method for preparing the cellulose composite aerogel from the waste paper according to the claim 1, characterized in that in the step 1.1, the drying temperature is 40-60 ℃, and the drying time is 12-24 h; the screen mesh of 300-400 meshes is adopted during sieving.
3. The method for preparing the cellulose composite aerogel from the waste paper according to claim 1, wherein in the step 1.3, the ultrasonic dispersion time is 1-2 h, and the mass ratio of the solid filter residue a to the ethanol is 1: 5 to 30.
4. The method for preparing the cellulose composite aerogel from the waste paper according to the claim 1, wherein in the step 1.4, the soaking time is 3-4 h, and the soaking temperature is 20-25 ℃; the drying temperature is 40-60 ℃, and the drying time is 12-24 h.
5. The method for preparing the cellulose composite aerogel from the waste paper according to the claim 1, wherein in the step 2.1, the time of ultrasonic dispersion is 1-2 h; the freezing temperature is-12 ℃ to-15 ℃, and the freezing time is 6h to 12 h.
6. The method for preparing the cellulose composite aerogel from the waste paper as claimed in claim 1, wherein in the step 2.3, the freeze-drying temperature is 55 ℃ and the freeze-drying time is 48-72 h.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443180A (en) * 2011-09-15 2012-05-09 复旦大学 Method for preparing cellulose composite aerogel
CN103980547A (en) * 2014-05-27 2014-08-13 哈尔滨工业大学 Method for preparing magnetic cellulose aerogel from wastepaper
CN105507059A (en) * 2014-09-22 2016-04-20 丹阳市华兴纸箱有限公司 Fiber packaging material preparation process
CN105733016A (en) * 2016-03-10 2016-07-06 云南中烟工业有限责任公司 Carbon-based polymer composite aerosol, preparation method of aerosol and application of aerosol in flue gas analysis
CN106589444A (en) * 2016-12-23 2017-04-26 福州大学 Method for preparing magnetic cellulose aerogel by utilizing waste paper

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443180A (en) * 2011-09-15 2012-05-09 复旦大学 Method for preparing cellulose composite aerogel
CN103980547A (en) * 2014-05-27 2014-08-13 哈尔滨工业大学 Method for preparing magnetic cellulose aerogel from wastepaper
CN105507059A (en) * 2014-09-22 2016-04-20 丹阳市华兴纸箱有限公司 Fiber packaging material preparation process
CN105733016A (en) * 2016-03-10 2016-07-06 云南中烟工业有限责任公司 Carbon-based polymer composite aerosol, preparation method of aerosol and application of aerosol in flue gas analysis
CN106589444A (en) * 2016-12-23 2017-04-26 福州大学 Method for preparing magnetic cellulose aerogel by utilizing waste paper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Green synthesis of hybrid graphene oxide/microcrystalline cellulose;Xiao Wei;《Journal of Hazardous Materials》;20170409;28-38页 *

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