CN112023897A - Preparation method of nanocellulose microspheres with selective adsorption and adsorption application of nanocellulose microspheres to dye wastewater - Google Patents

Preparation method of nanocellulose microspheres with selective adsorption and adsorption application of nanocellulose microspheres to dye wastewater Download PDF

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CN112023897A
CN112023897A CN202010903826.4A CN202010903826A CN112023897A CN 112023897 A CN112023897 A CN 112023897A CN 202010903826 A CN202010903826 A CN 202010903826A CN 112023897 A CN112023897 A CN 112023897A
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microspheres
cnf
dye
selective adsorption
freeze
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CN112023897B (en
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杨桂花
林兆云
陈嘉川
戢德贤
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Qilu University of Technology
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Qilu University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention relates to a preparation method of nano-cellulose microspheres with selective adsorbability and adsorption application of nano-cellulose microspheres to dye wastewater, and belongs to the field of preparation of bio-based materials. The preparation method comprises the following steps: adding the CNF suspension into HCl solution to form CNF microspheres; uniformly mixing the CNF microspheres and a silane coupling agent at 70-80 ℃, adding paraffin and Span-85 to react at 80-90 ℃ under the protection of inert gas, washing and freeze-drying to obtain a freeze-dried sample; and (3) refluxing, washing and drying the freeze-dried sample and the ionic liquid to obtain the nano-cellulose microspheres with selective adsorption. The adsorption selectivity of the modified CNF microspheres is adjusted by changing the pH of the dye solution, and the solid-to-liquid ratio of the CNF modified microspheres to the dye wastewater is 5-20 mg: 50 mL. f) And (4) recovering and recycling the CNF microspheres through centrifugal separation. The preparation method provided by the invention is simple, convenient to operate, strong in practicability, easy to recover and strong in environmental protection, and can solve the problem of water pollution in the current society.

Description

Preparation method of nanocellulose microspheres with selective adsorption and adsorption application of nanocellulose microspheres to dye wastewater
Technical Field
The invention belongs to the field of preparation of bio-based materials, and particularly relates to a preparation method of a nano-cellulose microsphere adsorption material.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The nano cellulose fiber (CNF) is a renewable polymer material with high strength and high mechanical property, and has rich sources. A large number of active hydroxyl groups exist on the surface of the CNF, which is beneficial to the mutual permeation and modification with a polymer matrix. How to prepare the degradable modified bio-based material by utilizing the characteristics of CNF, widening the application performance and improving the market value of the material is a problem to be solved at present.
The dye wastewater has various types, complex components, high pollutant content, certain color and great toxicity, so that the preparation of the material which has universality and can effectively treat the wastewater is difficult. The adsorption method has wide application in the aspect of organic wastewater treatment, but the cheap, efficient, renewable and degradable adsorption material is the focus of the research on the dye wastewater at present.
Disclosure of Invention
The invention provides a preparation method of CNF microspheres with selective adsorption to overcome the defects. CNF is used as a raw material to form microspheres in a salt solution, and ionic liquid is grafted on the surface of the microspheres, so that the microspheres have selective adsorption capacity, can be used for treating and recovering dye wastewater, and can provide a new direction for industrial application of CNF.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing nanocellulose microspheres with selective adsorption, comprising:
adding the CNF suspension into HCl solution to form CNF microspheres;
uniformly mixing the CNF microspheres and a silane coupling agent at 70-80 ℃, adding paraffin and Span-85 to react at 80-90 ℃ under the protection of inert gas, washing and freeze-drying to obtain a freeze-dried sample;
and (3) refluxing, washing and drying the freeze-dried sample and the ionic liquid to obtain the nano-cellulose microspheres with selective adsorption.
After the CNF is modified by adopting the method, the modified CNF microspheres can selectively adsorb anionic dye and cationic dye, and the nanocellulose is degradable and renewable, so that the modified CNF microspheres are green and pollution-free materials.
In a second aspect of the present invention, there is provided nanocellulose microspheres with selective adsorption prepared by any one of the above-mentioned methods.
The modified CNF microspheres have the capability of selectively adsorbing the dye, can be recovered through centrifugal separation, and are clean products.
In a third aspect of the invention, the application of the nano-cellulose microspheres with selective adsorption in treating dye wastewater is provided.
The modified nano cellulose microspheres are used for treating dye wastewater, so that the use of chemicals is reduced, and the treatment efficiency is improved, so that the modified nano cellulose microspheres are expected to be widely applied to treating dye wastewater.
The invention has the beneficial effects that:
(1) the invention takes CNF as raw material, and has the advantages of environmental protection and reproducibility.
(2) The modified CNF microspheres have the capability of selectively adsorbing the dye, can be recovered through centrifugal separation, and are clean products.
(3) The preparation method is simple, strong in adsorption capacity and strong in practicability, and has better economic and environmental benefits.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Interpretation of terms:
span-85 refers to sorbitan trioleate (Span 85).
Background art along with more and more attach importance to environmental problems, especially under the present condition that water resource is very deficient, handle sewage and be the must way of solving the quality of water problem. Therefore, the invention provides a preparation method of CNF microspheres for organic dye wastewater treatment.
One of the purposes of the invention is to provide a modification method of CNF microspheres.
The second purpose of the invention is to utilize the ionic liquid to modify the microspheres to achieve the purpose of selective adsorption.
The third purpose of the invention is to improve the recycling property of the CNF adsorbent.
The invention adopts the following technical scheme:
the preparation method of CNF microspheres with selective adsorption comprises the steps of preparing and modifying CNF microspheres as a raw material to ensure that the CNF microspheres have the capacity of selectively adsorbing impurities in wastewater;
in some embodiments, the modification method comprises the following specific steps: 10g of 0.8-1.5 wt% CNF suspension is taken, the pH is adjusted to neutral, and the CNF suspension is added dropwise into a slowly stirred 0.1mol/L HCl solution by using a needle tube with the range of 2.5mL and the needle diameter of 0.6 mm. After the end of the dropwise addition, 20 wt% of a silane coupling agent (relative to the mass of the CNF) was added dropwise, stirred at 70 ℃ for reaction for 2 hours, and then transferred to a three-necked flask in a water-oil ratio of 1: 2 adding paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. In thatAnd (3) refluxing the freeze-dried sample and the ionic liquid for 24 hours in a toluene solution, washing the reaction product for multiple times by using acetone and water after the reaction is finished, and drying the reaction product in vacuum to obtain the required CNF microspheres.
The specification of the CNF is not specially limited, in some embodiments, the CNF has a length of 500-2000 nm and a diameter of 10-50nm, and the obtained CNF microspheres have better adsorption capacity and mechanical properties.
In some embodiments, the CNF microspheres are prepared with a CNF concentration of 0.8 to 1.5 wt% so that the prepared microspheres have high density and are easily adsorbed;
the concentration of HCl is not particularly limited, and in some embodiments, the concentration of HCl used in the preparation of the CNF microspheres is 0.1mol/L, so as to effectively improve the dispersibility of CNF;
in some embodiments, the amount of the silane coupling agent loaded on the surface of the CNF microsphere is 20 wt%, and the silane coupling agent grafted on the surface of the CNF microsphere can improve the surface hydrophobicity of the CNF microsphere and couple the ionic liquid through the silane coupling agent;
in some embodiments, the silane coupling agent is selected to be 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-ethoxybromosilane, and the like, to better bind with the ionic liquid;
in some embodiments, paraffin and Span-85 are added simultaneously to a three-necked flask to react with CNF microspheres and the mass ratio of oil phase to water phase is 2: 1, to prevent cross-linking of the pellets;
in some embodiments, the ionic liquid is selected from 1-ethyl-3-methylimidazolium chloride salt, 1-butyl-3-methylimidazolium chloride salt and 1-butyl-3-methylimidazolium bromide salt, and the ionic liquid can further improve the adsorption performance of the CNF microspheres and realize selective adsorption;
in some embodiments, the CNF microspheres are modified with an ionic liquid in a ratio of 1: 2-2: 1. the finding shows that the dosage of the ionic liquid is continuously increased, the adsorption efficiency is reduced, and the dosage of the ionic liquid needs to be in a proper range and has a peak value;
in some embodiments, the selective adsorption comprises the following specific steps: mixing and stirring the modified CNF microspheres and dye wastewater for 1h, adjusting the adsorption selectivity of the modified CNF microspheres by changing the pH of a dye solution, and measuring the content change of adsorbed dye in the wastewater before and after adsorption by UV-Vis. After complete absorption, collecting the precipitate, centrifugally separating and recovering, desorbing with 10% ammonia water, washing with ethanol repeatedly, and drying for recycling.
In some embodiments, the solid-to-liquid ratio of CNF-modified microspheres to dye wastewater is 5-20 mg: 50mL to obtain better adsorption effect and removal rate.
In some embodiments, the dye wastewater is selected from organic cation dye light yellow 7GL, organic anion dye acid orange 7 and organic cation dye light yellow 7 GL/organic anion dye acid orange 7 mass ratio is 1: 1 in a liquid mixture.
In some embodiments, the CNF microspheres are recovered by centrifugal separation and recycled to achieve the purposes of environmental protection and reproducibility.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) 10g of a 1.0 wt% CNF suspension are taken, the pH is adjusted to neutral, and the CNF suspension is added dropwise to a slowly stirred 0.1mol/L HCl solution using a needle tube having a measuring range of 2.5mL and a needle diameter of 0.6 mm. After the dropwise addition is finished, dropwise addingAdding 20 wt% of 3-chloropropyltrimethoxysilane (relative to the mass of CNF), stirring at 70 ℃ for reaction for 2h, transferring into a three-neck flask, and mixing according to a water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried samples and 1-ethyl-3-methylimidazolium chloride salt were taken in a volume of 2: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) preparing a material with the mass ratio of 1: 1 of light yellow 7GL and acid orange 7, controlling the dye concentration to be 100mg/L, and determining that the obtained CNF microspheres reach a zero charge value when pHzp is 5.1. b) Adjusting the pH value of the dye solution to be less than pHzp to be 4.5, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 5.5, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1h at a ratio of 50mL, filtering the mixture by using a filter membrane after centrifugal separation, and measuring the content change of the adsorbed dye in the dye solution before and after adsorption by using UV-Vis.
Example 2
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) Taking 10g of 1.0 wt% CNF suspension, adjusting pH to neutral, adding dropwise CNF suspension into a needle tube with measuring range of 2.5mL and needle diameter of 0.6mm, and slowly stirring0.1mol/L HCl solution. After the dropwise addition, 20 wt% of 3-chloropropyltrimethoxysilane (relative to the mass of CNF) is added dropwise, the mixture is stirred at 70 ℃ for reaction for 2 hours and then transferred into a three-neck flask, and the reaction is carried out according to the water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried sample and 1-ethyl-3-methylimidazolium chloride salt were taken at a ratio of 1: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) preparing a material with the mass ratio of 1: 1 of light yellow 7GL and acid orange 7, controlling the dye concentration to be 100mg/L, and determining that the obtained CNF microspheres reach a zero charge value when pHzp is 5.5. b) Adjusting the pH value of the dye solution to be less than pHzp to be 5.0, and mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 6.0, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 3
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) 10g of a 1.0 wt% CNF suspension was taken, the pH was adjusted to neutral, the application range was 2.5mL, and the diameter of the needle was 0.6mmThe CNF suspension was added dropwise to a slowly stirring 0.1mol/L HCl solution. After the dropwise addition, 20 wt% of 3-chloropropyltrimethoxysilane (relative to the mass of CNF) is added dropwise, the mixture is stirred at 70 ℃ for reaction for 2 hours and then transferred into a three-neck flask, and the reaction is carried out according to the water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried sample and 1-ethyl-3-methylimidazolium chloride salt were taken at a ratio of 1: 2, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) 100mg/L of acid orange 7 solution was prepared, and the obtained CNF microspheres were determined to reach a zero charge value at pHzp of 5.9. b) Adjusting the pH value of the dye solution to be less than pHzp to be 5.0, and mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 6.5, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 4
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) 10g of 0.8 wt% CNF suspension is taken, pH is adjusted to be neutral, CNF is suspended by using a needle tube with the measuring range of 2.5mL and the needle diameter of 0.6mmThe solution was added dropwise to a slowly stirred 0.1mol/L HCl solution. After the dropwise addition, 20 wt% of 3-chloropropyltriethoxysilane (relative to the mass of CNF) is added dropwise, stirred at 70 ℃ for reaction for 2 hours and then transferred into a three-neck flask, and the reaction solution is stirred according to the water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried sample and 1-butyl-3-methylimidazolium chloride salt were taken in a volume ratio of 1: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) a bright yellow 7GL dye solution with the mass concentration of 100mg/L is prepared, and the obtained CNF microspheres reach a zero charge value when the pHzp is 5.3. b) Adjusting the pH value of the dye solution to be less than pHzp to be 4.5, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 6.0, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 5
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) Taking 10g of 1.0 wt% CNF suspension, adjusting pH to neutral, and introducing CNF into a needle tube with measuring range of 2.5mL and needle diameter of 0.6mmThe suspension was added dropwise to a slowly stirring 0.1mol/L HCl solution. After the dropwise addition, 20 wt% of 3-chloropropyltriethoxysilane (relative to the mass of CNF) is added dropwise, stirred at 70 ℃ for reaction for 2 hours and then transferred into a three-neck flask, and the reaction solution is stirred according to the water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried sample and 1-butyl-3-methylimidazolium chloride salt were taken in a volume ratio of 1: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) preparing a material with the mass ratio of 1: 1 of light yellow 7GL and acid orange 7, controlling the dye concentration to be 100mg/L, and determining that the obtained CNF microspheres reach a zero charge value when pHzp is 5.3. b) When the pH value of the dye solution is adjusted to be less than pHzp to be 4.5, the CNF microspheres and the dye solution are mixed according to the mixing ratio of 20 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; when the pH value of the dye solution is more than pHzp is 6.0, the CNF microspheres and the dye solution are mixed at the ratio of 20 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 6
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) The pH of a 10g suspension containing 1.2 wt% CNF was adjusted to neutral and the amount used wasTo a slowly stirring 0.1mol/L HCl solution, the CNF suspension was added dropwise through a 2.5mL needle having a 0.6mm needle diameter. After the end of the dropwise addition, 20 wt% of 3-ethoxy bromosilane (relative to the mass of CNF) was added dropwise, stirred at 70 ℃ for reaction for 2h and then transferred to a three-neck flask, and the reaction solution was stirred in a water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried samples and 1-butyl-3-methylimidazolium bromide were taken at a ratio of 1: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) a bright yellow 7GL dye solution with a concentration of 100mg/L was prepared, and the CNF microspheres obtained were determined to reach a zero charge value at a pHzp of 5.4. b) When the pH value of the dye solution is adjusted to be less than pHzp to be 4.8, the CNF microspheres and the dye solution are mixed according to the mixing ratio of 20 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; when the pH value of the dye solution is more than pHzp is 6.0, the CNF microspheres and the dye solution are mixed at the ratio of 20 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 7
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) A10 g suspension containing 1.5 wt% CNF was taken and the pH adjusted to neutral with a usage range of 2.5mL, 0.6mm needle diameter tube CNF suspension drop by drop into a slowly stirring 0.1mol/L HCl solution. After the dropwise addition, 20 wt% of 3-chloropropyltrimethoxysilane (relative to the mass of CNF) is added dropwise, the mixture is stirred at 70 ℃ for reaction for 2 hours and then transferred into a three-neck flask, and the reaction is carried out according to the water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried samples and 1-butyl-3-methylimidazolium chloride salt were taken in a volume ratio of 2: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) preparing a material with the mass ratio of 1: 1 of light yellow 7GL and acid orange 7, controlling the dye concentration to be 100mg/L, and determining that the obtained CNF microspheres reach a zero charge value when pHzp is 4.9. b) Adjusting the pH value of the dye solution to be less than pHzp to be 4.4, mixing the CNF microspheres and the dye solution in a ratio of 5 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 5.5, mixing the CNF microspheres and the dye solution in a ratio of 5 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 8
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) A1.5 wt% CNF suspension containing 10gThe pH of the suspension was adjusted to neutral, and the CNF suspension was added dropwise to a slowly stirred 0.1mol/L HCl solution using a 2.5mL needle tube with a 0.6mm needle diameter. After the dropwise addition, 20 wt% of 3-chloropropyltriethoxysilane (relative to the mass of CNF) is added dropwise, stirred at 70 ℃ for reaction for 2 hours and then transferred into a three-neck flask, and the reaction solution is stirred according to the water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried samples and 1-butyl-3-methylimidazolium chloride salt were taken in a volume ratio of 2: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) a bright yellow 7GL acid orange 7 dye solution with a concentration of 100mg/L was prepared, and the CNF microspheres obtained were determined to reach a zero charge value at a pHzp of 4.7. b) Adjusting the pH value of the dye solution to be less than pHzp to be 4.2, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 5.5, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Example 9
A preparation method of nano cellulose microspheres with selective adsorbability comprises the following specific steps:
1) preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding a proper amount of 64 wt% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) Taking a mixture containing 10g of 1.5wt% CNF suspension, pH adjusted to neutral, CNF suspension added dropwise to a slowly stirring 0.1mol/L HCl solution using a 2.5mL needle with a 0.6mm needle diameter. After the end of the dropwise addition, 20 wt% of 3-ethoxy bromosilane (relative to the mass of CNF) was added dropwise, stirred at 70 ℃ for reaction for 2h and then transferred to a three-neck flask, and the reaction solution was stirred in a water-oil ratio of 1: 2, adding the mixture into the reactor in a volume ratio of 1: 15 paraffin and Span-85 in N2Stirring and reacting for 2h at 80 ℃ under protection, washing with acetone and water for multiple times after the reaction is finished, and freeze-drying. e) In toluene solution, freeze-dried samples and 1-butyl-3-methylimidazolium bromide were taken in a volume ratio of 2: 1, refluxing for 24 hours, washing with acetone and water for multiple times after the reaction is finished, and drying in vacuum to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) preparing a material with the mass ratio of 1: 1 of light yellow 7GL and acid orange 7, controlling the dye concentration to be 100mg/L, and determining that the obtained CNF microspheres reach a zero charge value when pHzp is 4.8. b) When the pH value of the dye solution is adjusted to be less than pHzp to be 4.1, the CNF microspheres and the dye solution are mixed according to the mixing ratio of 20 mg: mixing and stirring the mixture for 1 hour according to the proportion of 50 mL; adjusting the pH value of the dye solution to be more than pHzp to be 5.5, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring at a ratio of 50mL for 1h, centrifuging, filtering with a filter membrane, and measuring the content change of adsorbed dye in the dye solution before and after adsorption by UV-Vis.
Comparative example 1
1) Preparing nano-cellulose: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding 64 wt% of concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell crusher, treating for 30min at 1200W power, homogenizing for 15min at the first stage valve pressure of 80bar and the second stage valve pressure of 350bar by a high-pressure homogenizer, and preparing CNF suspension with concentration of 1.0 wt%.
2) Adsorption of the dye in water by the nanocellulose: a) preparing a material with the mass ratio of 1: 1 light yellow 7GL and acid orange 7 mixed dye solution, dye concentration controlled at 100mg/L, CNF was determined to reach zero charge value at pHzp of 4.8. b) When the pH value of the dye solution is adjusted to be less than pHzp and is 4.0, mixing and stirring the CNF and the dye solution for 1 hour; adjusting the pH of the dye solution to pH > 5.0, mixing the CNF with the dye solution at a ratio of 10 mg: mixing and stirring the mixture for 1h at a ratio of 50mL, filtering the mixture by using a filter membrane after centrifugal separation, and measuring the content change of the adsorbed dye in the dye solution before and after adsorption by using UV-Vis.
Comparative example 2
1) Preparing nano cellulose microspheres: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking an appropriate amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a ratio of acid pulp to pulp of 18: 1 adding 64 wt% of concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, placing in an ultrasonic cell pulverizer, processing with 1200W power for 30min, homogenizing with a high-pressure homogenizer at a primary valve pressure of 80bar and a secondary valve pressure of 350bar for 15 min. d) Taking 10g of 1.0 wt% CNF suspension, adjusting the pH to be neutral, dropwise adding the CNF suspension into a slowly stirred 0.1mol/L HCl solution by using a needle tube with the range of 2.5mL and the needle diameter of 0.6mm, and freeze-drying to obtain the required CNF microspheres.
2) Selectively adsorbing the dye in water by the nano-cellulose microspheres: a) preparing a material with the mass ratio of 1: 1 of light yellow 7GL and acid orange 7, controlling the dye concentration to be 100mg/L, and determining that the obtained CNF microspheres reach a zero charge value at 4.6 when pHzp is. b) When the pH value of the dye solution is adjusted to be less than pHzp and is 4.0, mixing and stirring the CNF microspheres and the dye solution for 1 h; adjusting the pH value of the dye solution to be more than pHzp to be 5.0, mixing the CNF microspheres and the dye solution in a ratio of 10 mg: mixing and stirring the mixture for 1h at a ratio of 50mL, filtering the mixture by using a filter membrane after centrifugal separation, and measuring the content change of the adsorbed dye in the dye solution before and after adsorption by using UV-Vis.
And (3) performance testing:
the concentrations of the light yellow 7GL and acid orange 7 remaining in the dye solutions before and after the CNF treatment in comparative examples 1-2 and examples 1-9 were determined by an ultraviolet-visible spectrophotometer UV-Vis, using the concentrations of the light yellow 7GL and acid orange 7 in the solutions as performance test indices. The test method comprises the following steps: the dye solutions before and after the treatment were respectively placed in an ultraviolet-visible spectrophotometer to measure absorbance, and the concentration thereof was calculated according to a standard curve, with the test results shown in table 2.
TABLE 1 light yellow 7GL and acid orange 7 standards ultraviolet visible light absorbance
concentration/g/L of light yellow 7GL 0.0005 0.001 0.0015 0.002 0.0025
Absorbance/T1% 0.02286 0.03159 0.04033 0.04915 0.05805
Acid orange 7 concentration/g/L 0.0005 0.001 0.0015 0.002 0.0025
Absorbance/T2% 0.03144 0.03866 0.04571 0.05298 0.06014
According to calculation, the standard curve is Y1 ═ 17.588X1+ 0.014; y2 ═ 14.344X2+0.0243
Wherein X1 is the concentration of bright yellow 7GL in g/L; y1 is the absorbance of ultraviolet and visible light, T1%;
x2 is acid orange 7 concentration, g/L; y2 is the UV/Vis absorbance, T2%.
Table 2 adsorption performance of CNF microspheres prepared in examples 1 to 9 and comparative examples 1 and 2 to dye
Figure BDA0002660693460000171
It can be seen from table 2 that, after the CNF is modified by the method of the present invention, the modified CNF microspheres can selectively adsorb anionic dyes and cationic dyes, and the nanocellulose is degradable and renewable, and is a green pollution-free material.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. A method for preparing nano cellulose microspheres with selective adsorption is characterized by comprising the following steps:
adding the CNF suspension into HCl solution to form CNF microspheres;
uniformly mixing the CNF microspheres and a silane coupling agent at 70-80 ℃, adding paraffin and Span-85 to react at 80-90 ℃ under the protection of inert gas, washing and freeze-drying to obtain a freeze-dried sample;
and (3) refluxing, washing and drying the freeze-dried sample and the ionic liquid to obtain the nano-cellulose microspheres with selective adsorption.
2. The method for preparing nano-cellulose microspheres with selective adsorption property of claim 1, wherein the CNF suspension is prepared by sulfuric acid process combined with homogenization process.
3. The method for preparing nano-cellulose microspheres with selective adsorption of claim 1, wherein the concentration of the CNF suspension is 0.8-1.5 wt%.
4. The method for preparing nano-cellulose microspheres with selective adsorption property according to claim 1, wherein the silane coupling agent is at least one of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane and 3-ethoxybromosilane.
5. The method for preparing nano-cellulose microspheres with selective adsorption property of claim 1, wherein the silane coupling agent is added in an amount of 20-25 wt% of CNF.
6. The method for preparing nano-cellulose microspheres with selective adsorption property according to claim 1, wherein the ionic liquid is at least one of 1-ethyl-3-methylimidazolium chloride salt, 1-butyl-3-methylimidazolium chloride salt and 1-butyl-3-methylimidazolium bromide salt.
7. The method for preparing nano-cellulose microspheres with selective adsorption property according to claim 1, wherein the dosage ratio of the freeze-dried sample to the ionic liquid is 1-2: 1 to 2.
8. The method for preparing nano-cellulose microspheres with selective adsorption property according to claim 1, wherein the mass ratio of the oil phase to the water phase is 2-4: 1 Paraffin and Span-85 were added.
9. Nanocellulose microspheres with selective adsorption prepared by the method of any one of claims 1-8.
10. Use of nanocellulose microspheres with selective adsorption of claim 9 for the treatment of dye wastewater.
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