CN112982003A - Method for preparing modified nano-cellulose by ternary eutectic solvent system - Google Patents
Method for preparing modified nano-cellulose by ternary eutectic solvent system Download PDFInfo
- Publication number
- CN112982003A CN112982003A CN202110326794.0A CN202110326794A CN112982003A CN 112982003 A CN112982003 A CN 112982003A CN 202110326794 A CN202110326794 A CN 202110326794A CN 112982003 A CN112982003 A CN 112982003A
- Authority
- CN
- China
- Prior art keywords
- eutectic solvent
- ternary eutectic
- solvent system
- preparing
- cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002904 solvent Substances 0.000 title claims abstract description 55
- 230000005496 eutectics Effects 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229920002678 cellulose Polymers 0.000 title claims abstract description 28
- 239000001913 cellulose Substances 0.000 title claims abstract description 28
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 22
- 238000000265 homogenisation Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229920001131 Pulp (paper) Polymers 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 8
- 235000019743 Choline chloride Nutrition 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 8
- 229960003178 choline chloride Drugs 0.000 claims description 8
- 238000012824 chemical production Methods 0.000 claims description 4
- 239000013501 sustainable material Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims 2
- 238000012986 modification Methods 0.000 abstract description 10
- 230000004048 modification Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 241000219927 Eucalyptus Species 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 238000013478 data encryption standard Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- -1 packaging Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
- D21B1/34—Kneading or mixing; Pulpers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the field of lignocellulose materials, and provides a method for preparing modified nanocellulose by a ternary eutectic solvent system. The method combines the superfine grinding treatment and the high-pressure homogenization treatment while pretreating the modified cellulose by the eutectic solvent, and is a method for efficiently preparing the sulfonated modified CNF. The method has the advantages of simple operation and low cost, can effectively reduce energy loss of mechanical treatment, has good modification effect on the cellulose nanofibrils, can recycle the used eutectic solvent, is environment-friendly, and is beneficial to industrial production of the sulfonated modified CNF.
Description
Technical Field
The invention belongs to the field of lignocellulose materials, and particularly relates to a method for preparing modified nanocellulose by using a ternary eutectic solvent system.
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.
In recent years, the separation of nano-sized cellulose fibers from natural cellulose fibers has attracted a great interest in the field of sustainable materials and chemical production. Cellulose Nanofibrils (CNF) exhibit better properties including high stiffness and strength and larger surface area than other micron-sized analogues. The excellent performance of the nano-cellulose can be used for producing flexible and light green electronic products. Nanocellulose materials are also a source of available biodegradable chemicals. Several methods for preparing unmodified nanocellulose include purely mechanical methods, enzymatic methods, and solvent pretreatment methods. However, chemical modification of natural cellulose fibers prior to CNF production can improve the quality of nanocellulose (e.g., more uniform particle size distribution) and improve its properties, such as ion exchange capacity, stability and dispersibility. Furthermore, chemical pretreatment can significantly reduce the energy consumption of CNF during the preparation process.
Solvents are one of the major sources of chemical contamination and waste during chemical and material synthesis. While conventional molecular solvents are endothermic and provide uniform reaction conditions, they are often volatile, flammable, toxic, or otherwise harmful. Novel solvent systems such as ionic liquids have been proposed as environmentally friendly alternatives to traditional solvents. Eutectic Solvents (DESs) are ionic liquid analogs (sometimes classified as a subset of ionic liquids) and are considered as potential replacements for traditional molecular solvents. Like ionic liquids, DESs have lower vapor pressures, exhibit good dissolution potential, and are, in certain cases, recyclable. DESs are studied as solvents, reagents and catalysts in organic synthesis and biomass processing.
DES can swell and even dissolve cellulose, so DES treatment can be used as an effective pretreatment means for preparing nano-cellulose, surface functional groups can be introduced, the appearance of a final product can be controlled by adjusting process conditions, and the energy consumption of subsequent mechanical treatment can be reduced; compared with ionic liquid, DES is a more green and safe solvent, and is easier to recover and reuse, thereby ensuring the cleanness of the preparation process of the nano-cellulose and reducing the production cost. The CNF modified by the eutectic solvent is a chemical grafting modification method, has the excellent characteristics of the chemical grafting modification method, has the advantages of simple operation, low cost, small pollution to the environment, recoverability of the used eutectic solvent and the like, is suitable for industrial production of the modified CNF, and has wide application prospect.
Disclosure of Invention
In order to overcome the defects of the current modified CNF preparation technology, the invention provides a method for preparing modified nano-cellulose by using a novel ternary eutectic solvent system. Compared with the traditional method, the method has the advantages of simple operation, low energy loss and little environmental pollution, and can effectively improve the preparation technology of the modified CNF.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a method for preparing modified nanocellulose by using a ternary eutectic solvent system is provided, which comprises the following steps:
pretreating the paper pulp raw material by adopting a ternary eutectic solvent; stopping the reaction, and separating from the mixed liquid;
and carrying out superfine grinding and high-pressure homogenization on the paper pulp fiber to obtain the modified nanocellulose.
The research finds that: the existing method for preparing CNF by high-pressure homogenization has the problems that the slurry is easy to block a machine and the energy consumption is too high, and the industrial popularization of the CNF is limited. Therefore, the invention carries out long-term analysis and experimental groping and discovers that: the adopted 'superfine grinding and high-pressure homogenization' treatment replaces single high-pressure homogenization treatment and has two main advantages: 1. the homogenization treatment after the superfine grinding can realize the preparation of CNF with higher concentration (1 percent) and can not cause the condition that the slurry blocks the machine and the like in the high-pressure homogenization process. 2. The energy consumption of the whole preparation process can be obviously reduced by carrying out superfine grinding pretreatment before homogenization, and the energy consumption of a high-pressure homogenizer is about 1000 times of that of a superfine grinder under the same working time.
In a second aspect of the invention, there is provided a modified nanocellulose prepared by any of the above methods.
According to the method, the pulp raw material is pretreated by using the eutectic solvent modification, so that the sulfonation modification treatment is realized while swelling cellulose, the energy loss of subsequent treatment of an ultrafine pulverizer and a high-pressure homogenizer is greatly reduced, and the sulfonated CNF with a good modification effect is successfully prepared.
In a third aspect of the invention, the application of the modified nanocellulose in the fields of sustainable materials, chemical production and green electronic products is provided.
The modified nano-cellulose prepared by the method has a good sulfonation effect and low energy loss, so that the modified nano-cellulose is expected to be widely applied to the fields of sustainable materials, chemical production and green electronic products.
The invention has the beneficial effects that:
(1) according to the method, the pulp raw material is pretreated by using the eutectic solvent modification, so that the sulfonation modification treatment is realized while swelling cellulose, the energy loss of subsequent treatment of an ultrafine pulverizer and a high-pressure homogenizer is greatly reduced, and the sulfonated CNF with a good modification effect is successfully prepared.
(2) The preparation method disclosed by the invention is simple to operate, low in cost, green and environment-friendly, does not use any external solvent, can obtain the modified CNF with high performance and high yield only through pretreatment and mechanical treatment of the eutectic solvent, reduces the energy loss, enlarges the application range of the CNF, and the used eutectic solvent can be recovered through methods such as rotary evaporation and the like, so that the CNF can be recycled, and the method is favorable for industrial production of the modified CNF.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a flow chart of an experiment according to the present invention.
Fig. 2 is a scanning electron microscope image of the modified CNF provided in example 4 of the present invention.
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.
As described above, the conventional chemical modification method of CNF is complicated in operation, high in cost, and has an environmental pollution problem.
In view of this, in one embodiment of the present invention, there is provided a method for preparing a modified nanocellulose based on a reactive eutectic solvent, the method comprising:
(1) preparing a eutectic solvent: synthesizing eutectic solvent by sulfamic acid, urea and choline chloride;
(2) pretreatment of eutectic solvent: adding a paper pulp raw material into the eutectic solvent system in the step (1);
(3) separating the treated pulp fiber: adding deionized water into the reaction system in the step (2) to terminate the reaction, and then washing and filtering out the pulp fibers;
(4) and (3) processing by an ultrafine pulverizer: preparing the paper pulp fibers separated in the step (3) into a fiber suspension with a certain pulp concentration, and then carrying out crushing treatment by using an ultrafine crusher.
(5) High-pressure homogenization treatment: and (4) carrying out high-pressure homogenization treatment on the slurry obtained after the superfine grinding in the step (4) for a certain number of times to obtain the sulfonated and modified CNF.
In another embodiment of the invention, the molar ratio of the mixture of sulfamic acid, urea and choline chloride is 1:2: 1-1: 3:1, the reaction temperature is 50-60 ℃, and the mixing time is 0.5-2 h;
in another embodiment of the present invention, the pulp material is bleached chemical eucalyptus pulp;
the cellulose content of the bleached chemical eucalyptus pulp is 84-86%;
the paper pulp raw material is dried before the eutectic solvent is added;
the drying treatment conditions are as follows: drying for 24-26 h at 40-60 ℃;
the molar ratio of the pulp raw material cellulose pretreated by the eutectic solvent to the sulfamic acid is 1: 6-1: 15, the pretreatment temperature is 90-100 ℃, and the pretreatment time is 0.5-2 h.
In another embodiment of the present invention, the slurry concentration is 0.8 to 1.0%;
the number of times of treatment by the ultrafine grinder is 1-5;
the number of times of treatment by using the high-pressure homogenizer is 1-5;
the modified CNF is sulfonated CNF.
In still another embodiment of the present invention, there is provided sulfonated CNF obtained by the above modification method.
In another embodiment of the present invention, the sulfonated CNF is used in the fields of flexible and lightweight green electronic products, plastics, packaging, paper making, medicine, etc.
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
(1) Drying in an oven: drying bleached chemical eucalyptus pulp in an oven at 40 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid, urea and choline chloride in a molar ratio of 1:2:1, and mixing for 2 hours at 50 ℃ by adopting a water bath heating mode;
(3) pretreatment of eutectic solvent: adding the dried bleached chemical eucalyptus pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical eucalyptus pulp cellulose to the sulfamic acid is 1:10, and treating for 0.5h at 100 ℃;
(4) separating the treated pulp fibers: adding deionized water into the reaction system in the step (3) to terminate the reaction, and then washing and filtering out the pulp fibers;
(5) and (3) processing by an ultrafine pulverizer: preparing the paper pulp fibers separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 1 time, wherein the particle size of the ultrafine crushed cellulose is 3-6 microns;
(6) high-pressure homogenization treatment: and (3) carrying out high-pressure homogenization treatment on the slurry obtained after the superfine grinding in the step (5), wherein the treatment frequency is 5 times, the treatment condition is that the pressure is 20MPa, and the treatment time is 35 min.
The modified CNF prepared in this example had a degree of substitution of 0.01, a potential of-30.83, and an energy consumption of 2.11X 107KJ/Kg (see Table 1).
Example 2
(1) Drying in an oven: drying bleached chemical eucalyptus pulp in an oven at 60 ℃ for 26 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid, urea and choline chloride in a molar ratio of 1:3:1, and mixing for 2 hours at 50 ℃ by adopting a water bath heating mode;
(3) pretreatment of eutectic solvent: adding the dried bleached chemical eucalyptus pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical eucalyptus pulp cellulose to the sulfamic acid is 1:10, and treating for 1h at 100 ℃;
(4) separating the treated pulp fibers: adding deionized water into the reaction system in the step (3) to terminate the reaction, and then washing and filtering out the pulp fibers;
(5) and (3) processing by an ultrafine pulverizer: preparing the paper pulp fibers separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 1 time, wherein the particle size of the ultrafine crushed cellulose is 2-5 microns;
(6) high-pressure homogenization treatment: and (3) carrying out high-pressure homogenization treatment on the slurry obtained after the superfine grinding in the step (5), wherein the treatment frequency is 5 times, the treatment condition is that the pressure is 20MPa, and the treatment time is 27 min.
The degree of substitution of the modified CNF prepared in this example was 0.118, the Zeta potential was-34.43, and the energy consumption was 1.63X 107KJ/Kg (see Table 1).
Example 3
(1) Drying in an oven: drying bleached chemical eucalyptus pulp in an oven at 50 ℃ for 26 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid, urea and choline chloride in a molar ratio of 1:2:1, and mixing for 2 hours at 60 ℃ by adopting a water bath heating mode;
(3) pretreatment of eutectic solvent: adding the dried bleached chemical eucalyptus pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical eucalyptus pulp cellulose to the sulfamic acid is 1:10, and treating for 2 hours at 100 ℃;
(4) separating the treated pulp fibers: adding deionized water into the reaction system in the step (3) to terminate the reaction, and then washing and filtering out the pulp fibers;
(5) and (3) processing by an ultrafine pulverizer: preparing the paper pulp fibers separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 1 time, wherein the particle size of the ultrafine crushed cellulose is 2-4 microns;
(6) high-pressure homogenization treatment: and (3) carrying out high-pressure homogenization treatment on the slurry obtained after the superfine grinding in the step (5), wherein the treatment frequency is 5 times, the treatment condition is that the pressure is 20MPa, and the treatment time is 26 min.
The modified CNF prepared in this example had a degree of substitution of 0.12, a Zeta potential of-35.68, and an energy consumption of 1.61X 107KJ/Kg (see Table 1).
Example 4
(1) Drying in an oven: drying bleached chemical eucalyptus pulp in an oven at 50 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid, urea and choline chloride in a molar ratio of 1:3:1, and mixing for 2 hours at 60 ℃ by adopting a water bath heating mode;
(3) pretreatment of eutectic solvent: adding the dried bleached chemical eucalyptus pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical eucalyptus pulp cellulose to the sulfamic acid is 1:10, and treating for 2 hours at 100 ℃;
(4) separating the treated pulp fibers: adding deionized water into the reaction system in the step (3) to terminate the reaction, and then washing and filtering out the pulp fibers;
(5) and (3) processing by an ultrafine pulverizer: preparing the paper pulp fibers separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 1 time, wherein the particle size of the ultrafine crushed cellulose is 1-3 microns;
(6) high-pressure homogenization treatment: and (4) carrying out high-pressure homogenization treatment on the slurry obtained after the superfine grinding in the step (5), wherein the treatment frequency is 5 times, the treatment condition is that the pressure is 20MPa, and the treatment time is 25 min.
The degree of substitution of the modified CNF prepared in this example was 0.14, the Zeta potential was-38.63, and the energy consumption was 1.56X 107KJ/Kg (see Table 1).
TABLE 1 characterization results of examples 1-4 modified cellulose
| Degree of substitution | Zeta potential/mV | Energy consumption x 107KJ/Kg | |
| Example 1 | 0.01 | -30.83 | 2.11 |
| Example 2 | 0.12 | -30.43 | 1.63 |
| Example 3 | 0.12 | -35.68 | 1.61 |
| Example 4 | 0.14 | -38.63 | 1.56 |
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 modified nano-cellulose by a ternary eutectic solvent system is characterized by comprising the following steps:
pretreating the paper pulp raw material by adopting a ternary eutectic solvent; stopping the reaction, and separating from the mixed liquid;
and carrying out superfine grinding and high-pressure homogenization on the paper pulp fiber to obtain the modified nanocellulose.
2. The method for preparing the modified nanocellulose according to the ternary eutectic solvent system of claim 1, wherein said modified nanocellulose is sulfonated nanocellulose.
3. The method for preparing modified nanocellulose by using the ternary eutectic solvent system according to claim 1, wherein the number of times of treatment by the high-pressure homogenizer is 1-5, and preferably, the slurry concentration is 0.8-1.0%.
4. The method for preparing modified nanocellulose by using the ternary eutectic solvent system according to claim 1, wherein the number of times of treatment by the ultrafine pulverizer is 1-5, and preferably, the slurry concentration is 0.8-1.0%.
5. The method for preparing modified nanocellulose by using the ternary eutectic solvent system as claimed in claim 1, wherein the pulp raw material is dried before the eutectic solvent is added.
6. The method for preparing the modified nanocellulose by using the ternary eutectic solvent system according to claim 5, wherein the drying is performed under the specific condition of drying at 40-60 ℃ for 24-26 h.
7. The method for preparing modified nanocellulose by using the ternary eutectic solvent system as claimed in claim 1, wherein the ternary eutectic solvent is prepared from sulfamic acid, urea and choline chloride;
preferably, the mixing molar ratio of the sulfamic acid to the urea to the choline chloride is 1:2: 1-1: 3:1, the reaction temperature is 50-60 ℃, and the mixing time is 0.5-2 hours;
preferably, the molar ratio of the pulp raw material cellulose to the sulfamic acid is 1: 6-1: 15, the pretreatment temperature is 90-100 ℃, and the pretreatment time is 0.5-2 h.
8. The method for preparing modified nanocellulose by using the ternary eutectic solvent system as claimed in claim 1, wherein the pulp raw material is bleached chemical eucalyptus pulp;
preferably, the bleached chemical eucalyptus pulp has a cellulose content of 84-86%.
9. A modified nanocellulose prepared by the process of any one of claims 1-8.
10. Use of the modified nanocellulose as claimed in claim 9 in the fields of sustainable materials, chemical production and green electronics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110326794.0A CN112982003A (en) | 2021-03-26 | 2021-03-26 | Method for preparing modified nano-cellulose by ternary eutectic solvent system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110326794.0A CN112982003A (en) | 2021-03-26 | 2021-03-26 | Method for preparing modified nano-cellulose by ternary eutectic solvent system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112982003A true CN112982003A (en) | 2021-06-18 |
Family
ID=76333898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110326794.0A Pending CN112982003A (en) | 2021-03-26 | 2021-03-26 | Method for preparing modified nano-cellulose by ternary eutectic solvent system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112982003A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323826A (en) * | 2022-08-26 | 2022-11-11 | 华南理工大学 | Tough high-transmittance paper and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568730A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Method for preparing renewable nano-celluloses |
| CN109024039A (en) * | 2017-06-09 | 2018-12-18 | 天津科技大学 | A kind of preparation method of the nano-cellulose of type containing lignin gel |
| CN109235102A (en) * | 2018-10-25 | 2019-01-18 | 齐鲁工业大学 | A kind of method of eutectic solvent pretreatment preparation cellulose nanometer fibril |
| CN110540508A (en) * | 2019-08-30 | 2019-12-06 | 齐鲁工业大学 | Eutectic solvent and application thereof in extracting lignin |
| CN111187356A (en) * | 2020-03-25 | 2020-05-22 | 齐鲁工业大学 | Method for preparing microcrystalline cellulose by treating poplar wood powder with eutectic solvent and acid |
| CN111471113A (en) * | 2020-06-16 | 2020-07-31 | 天津科技大学 | Preparation method of Cellulose Nanofibrils (CNF) |
| CN112175095A (en) * | 2020-10-30 | 2021-01-05 | 齐鲁工业大学 | Method for sulfonating modified cellulose by ternary eutectic solvent system |
| CN112267157A (en) * | 2020-10-29 | 2021-01-26 | 齐鲁工业大学 | Preparation method of cellulose nano-fibrils modified based on reactive eutectic solvent |
-
2021
- 2021-03-26 CN CN202110326794.0A patent/CN112982003A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568730A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Method for preparing renewable nano-celluloses |
| CN109024039A (en) * | 2017-06-09 | 2018-12-18 | 天津科技大学 | A kind of preparation method of the nano-cellulose of type containing lignin gel |
| CN109235102A (en) * | 2018-10-25 | 2019-01-18 | 齐鲁工业大学 | A kind of method of eutectic solvent pretreatment preparation cellulose nanometer fibril |
| CN110540508A (en) * | 2019-08-30 | 2019-12-06 | 齐鲁工业大学 | Eutectic solvent and application thereof in extracting lignin |
| CN111187356A (en) * | 2020-03-25 | 2020-05-22 | 齐鲁工业大学 | Method for preparing microcrystalline cellulose by treating poplar wood powder with eutectic solvent and acid |
| CN111471113A (en) * | 2020-06-16 | 2020-07-31 | 天津科技大学 | Preparation method of Cellulose Nanofibrils (CNF) |
| CN112267157A (en) * | 2020-10-29 | 2021-01-26 | 齐鲁工业大学 | Preparation method of cellulose nano-fibrils modified based on reactive eutectic solvent |
| CN112175095A (en) * | 2020-10-30 | 2021-01-05 | 齐鲁工业大学 | Method for sulfonating modified cellulose by ternary eutectic solvent system |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323826A (en) * | 2022-08-26 | 2022-11-11 | 华南理工大学 | Tough high-transmittance paper and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Towards sustainable production and utilization of plant-biomass-based nanomaterials: a review and analysis of recent developments | |
| CN105646721A (en) | Preparation method of nanocellulose fibrils | |
| FI127918B (en) | Method of dewatering water soluble polymers | |
| Luo et al. | Preparation and characterization of nanocellulose fibers from NaOH/urea pretreatment of oil palm fibers | |
| CN108350090B (en) | Cellulose xanthate nanofibers | |
| CN112267157A (en) | Preparation method of cellulose nano-fibrils modified based on reactive eutectic solvent | |
| CN107602709B (en) | Clean preparation method of carboxymethyl nano-cellulose material | |
| CN105713099A (en) | Method combining formic acid preprocessing and high-pressure homogenization to prepare nano-crystalline cellulose fibrils | |
| Palacios Hinestroza et al. | Isolation and characterization of nanofibrillar cellulose from Agave tequilana Weber bagasse | |
| Islam et al. | Effect of low pressure alkaline delignification process on the production of nanocrystalline cellulose from rice husk | |
| CN109235102A (en) | A kind of method of eutectic solvent pretreatment preparation cellulose nanometer fibril | |
| CN109467741B (en) | Method for separating and recycling waste polyester-cotton textiles through hydrothermal reaction catalyzed by organic acid | |
| CN108822315A (en) | A kind of high-strength transparent hydrophobic cellulose nanometer film and preparation method thereof | |
| AU2020100319A4 (en) | Method for preparing cellulose nanofibrils by deep eutectic solvent pretreatment | |
| Liu et al. | Dissolution of cellulose from AFEX-pretreated Zoysia japonica in AMIMCl with ultrasonic vibration | |
| CN107881842A (en) | A kind of method that high-strength corrugated base paper is prepared using stalk and secondary stock | |
| Culsum et al. | Isolation and characterization of cellulose nanocrystals (CNCs) from industrial denim waste using ammonium persulfate | |
| JP7056987B1 (en) | Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner | |
| Yeganeh et al. | The effect of Sulfuric acid and Maleic acid on characteristics of nano-cellulose produced from waste office paper | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| CN112982003A (en) | Method for preparing modified nano-cellulose by ternary eutectic solvent system | |
| CN108892786B (en) | Lignin/surfactant composite nano particle and preparation method thereof | |
| Wu et al. | Integrated and sustainable preparation of functional nanocellulose via formic acid/choline chloride solvents pretreatment | |
| Du et al. | Cellulose nanocrystals prepared by persulfate one-step oxidation of bleached bagasse pulp | |
| Jančíková et al. | The role of deep eutectic solvents in the production of cellulose nanomaterials from biomass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210618 |
|
| RJ01 | Rejection of invention patent application after publication |